Tay 2003

Solid freeform fabrication of ceramics
B. Y. Tay, J. R. G. Evans and M. J. Edirisinghe
troversially that some processes may be materials

Solid freeforming is a genus of manufacturing speci c. It seems that the taxonomy of manufacturing
processes in which three-dimensional objects are processes is not well organised from the student’s
assembled by point, line or planar addition of point of view and awaits completion. In the casting
material. Confining surfaces, such as mould or die category, which embraces sand casting, die casting,
walls, are absent. The shape is built by adding injection moulding, solvent casting, slip casting and
rather than subtracting material. Solid freeforming microcasting methods such as LIGA (Lithogra e–
has come to be computer controlled over the past Galvanoformung–Abformung), a change of state
two decades in parallel with the expansion of the
occurs against con ning surfaces that de ne the shape.
data handling capacity of personal computers. It
can be used for rapid prototyping but also offers The range of state change methods includes phase
mass production pathways in which individuation change, solvent evaporation, chemical reaction and
is possible. It is of particular interest for the phase separation. In deformation methods, dies, rolls
creation, inter alia, of prosthetics that can be and formers are used for compaction, drawing,
individually built from modified X-ray computed forging, rolling and spinning. Most of these processes
tomographic data. Some routes offer the are now enhanced by computer control. Machining
additional capability to control, from the computer, operations include carving, turning, milling, electro-
not just the shape but also the composition discharge machining, laser machining and etching,
throughout a component. Thus, three-dimensional while joining methods such as welding, soldering,
functional gradients in multiphase ordered
brazing, adhesive bonding and the use of fasteners
composites become possible. The concept of
‘design’ now embraces the integration of the allow prefabricated components to be assembled to
spatial variation of composition, microstructure achieve a higher level of complexity.
and hence of properties together with the shape Some processes are missing from this list. The
parameters for multifunctional materials. This is a creation of a coiled pot from clay can be dated to the
vast and expanding field in which the first 5th millennium BC.7 It does not t these categories
textbooks are emerging. A review of this type must but is the historical antecedent of a solid freeforming
necessarily be focused. The emphasis here process known as ‘fused deposition modelling’ (q.v.)
therefore is placed on ceramic processing. This in which the computer controlled travel of an extruder
review attempts to set out the taxonomy of solid nozzle builds a shape from linear extrudate.8 It is also
freeforming in an historical context, disentangling
not quite so easy to classify brickwork. Houses are
the multiplicity of process names that have arisen
over the past two decades. Special emphasis is not made by building a large block of masonry and
placed on multilayer printing methods, because machining away the living space. Neither are they
they have tended to be neglected in popular made by casting a mass of bricks and mortar into
reviews, and upon applications in the medical shuttering. Instead the design of the house is ‘sliced’
arena, because they, among all possible into layers known as courses and each course is
applications, demand the individuation that solid assembled ‘point-by-point’ in units called bricks. This
freeforming can offer. IMR/396 is solid freeforming. Archaeologists have dated evi-
dence of well established masonry found in Egyptian
At the time the work was carried out the authors were excavations to the 4th millennium BC.9
in the Department of Materials, Queen Mary, University
of London, Mile End Road, London E1 4NS, UK (m.j. Indeed solid freeforming can be traced further back
edirisinghe@qmul.ac.uk). Dr Tay is now with SIM Tech, to the earliest forms of cellular life, at around 3·5
Singapore. billion years.10 Most forms of hard and soft tissue in
© 2003 IoM Communications Ltd and ASM International. biological systems are built cell-by-cell or plane-by-
Published by Maney for the Institute of Materials, Minerals plane. In a sense then, solid freeforming provides a
and Mining and ASM International. conceptual link between conventional volume manu-
facturing and so called ‘biomimetic’ materials pro-
cessing in which nature’s construction methods are
mimicked for the preparation of engineered arte-
Introduction facts;11 it is related to morphogenesis. The signi cant
Manufacturing processes development in recent years is that computers have
To appreciate solid freeforming it is helpful to com- been enabled to execute solid freeforming procedures
pare it with the other manufacturing classes. Scholars in much the same way that they control forging tools,
of manufacturing processes tend to classify methods machine tools, injection moulding, welding processes
of shaping materials into four principal categories and the robotic application of adhesives in the other
and these are reiterated in popular manufacturing manufacturing classes.
texts1–4 as: (i) casting, (ii) deformation, (iii) machin-
ing, and (iv) joining. Some authors add a chapter
entitled ‘others’ as a repository for processes that just Terminology
do not seem to t,3,4 while some mix processes and The three factors that distinguish solid freeforming
materials in their chapter headings5,6 suggesting con- are: (i) the material is added to rather than subtracted
DOI 10.1179/095066003225010263 International Materials Reviews 2003 Vol. 48 No. 6 341
342 Tay et al. Solid freeform fabrication of ceramics
from the component, (ii) the shaping operation is not

reliant on con ning surfaces such as a mould wall,
roller or anvil, and (iii) the shape is created incremen-
tally. This leads to the following de nition of solid
freeform fabrication: T he creation of a three-dimen-
sional shape by point, line or planar addition of material
without the use of con ning surfaces other than a base.
Solid freeforming is not the only name used to
describe this genus. One of the earliest applications
of computer control to solid freeforming produced
stereolithography (q.v.) which oVered the capability
to download a computer aided design (CAD) le into
three-dimensional form in a matter of hours and
the term ‘rapid prototyping’ appeared. Prototyping 1 Growth of memory of personal computers
allows a designer to check the appearance and func- 1980–2002: logarithm of RAM bytes (based
tion of a part before a signi cant investment in tooling on desktop facilities available to staff in
is made. Rapid prototyping (RP) was de ned as the Department of Materials, Queen Mary,
‘fast production of prototype models’ 12 but has grown University of London)
to embrace a set of manufacturing processes and
associated information technology. These enable pre- compositional data are stored in conjunction with
cise, robust and functional solid prototypes to be shape data for the preparation of functionally graded
created quickly and directly from CAD les with little materials. For this reason novel ways of giving the
need for human intervention.13 This has resulted personal computer a manufacturing capability are
in greater freedom for designers to obtain three- steadily emerging. In many instances the performance
dimensional representations of their drawings more of manufacturing peripherals now lags behind the
frequently, to facilitate checking of assembly and graphics handling capability of personal computers.
function, and has led to substantial reductions in Solid freeforming technology is boosted by an
product development cost and lead times. In contrast, electronic database produced by CAD modelling,
the traditional pattern maker who had served the computed tomography (CT) scanning or laser digitis-
foundry industry by skilfully converting an engineering to de ne the tool path, while speci c materials
ing drawing into a wooden pattern often took several such as uids, powders, wires or laminates are applied
weeks. concurrently or deposited in layers in advance.13
Subsequently, it became clearer that many of these These characteristics make solid freeforming suitable
processes could become manufacturing pathways in
for fabricating geometrically complex components,
their own right and be used to make components14
eliminating the tooling set up which is necessary for
so the term ‘rapid manufacturing’ was used to describe
numerical control machining. They generally mini-
these processes.15,16 This is a diYcult title to sanction,
mise or eliminate material waste.
since a complex plastic shape made by stereolithogra-
The adjectives ‘direct’ and ‘indirect’ are applied to
phy could take 1–2 h to build but be injection
most of the solid freeforming processes. The distinc-
moulded in 1–2 s. It is not a term used in this review.
tion is important, but sometimes not very obvious,
The terms ‘layered manufacturing’, ‘automated fabri-
cation’, ‘desktop manufacturing’ and ‘fast free-form and unfortunately does not have the same meaning
fabrication’ are alternatives.13 Solid freeforming for each process. Examples may help: in the case of
‘addresses the rapid creation of models, prototypes, stereolithography and fused deposition modelling,
patterns and limited run manufacturing’ for the pro- ‘indirect’ means that the process is used to make
duction of ‘complex freeform solid objects directly special moulds that will de ne the shape of the target
from a computer model of an object without part- material, rather than directly shaping the material
speci c tooling or knowledge’.17 that is sought. These approaches are illustrated with
Some of the terms have a strong promotional dramatic pictures of artefacts by Bauer and Knitter.21
content such as ‘desktop manufacturing’, ‘ exible In the case of selective laser sintering, ‘indirect’ means
manufacturing’18 and ‘art to part technology’19 but that a lower melting point fugitive binder, precursor
oVer little of descriptive value to the scholar. ‘Layered or component of the nal material is melted by the
manufacturing’20 presents more realism but conceals laser to hold powder together for nal conventional
the capability to achieve point-by-point or line-by- sintering. In the case of ink-jet printing, ‘direct’ means
line control of microstructure oVered inter alia by the that the powder in the form of a suspension passes
more recent jet printing methods or by extrusion through the printhead to freeform the shape and
freeforming methods respectively. It is thus a restric- ‘indirect’ means that binder is printed onto pre-
tive title. placed powder.
The emergence of solid freeforming in the past two As solid freeforming processes proliferated, the
decades is attributable principally to the growth of student of manufacturing processes had to contend
the memory capacity of desktop computers (Fig. 1) both with dissimilar names applied to identical pro-
which has been approximately doubling each year in cesses and with a multitude of acronyms seemingly
rough correspondence to Moore’s law. The software devised to obscure the methodology. Both these
and storage capability now outstrip the speed and impediments emerge from the attempt to claim and
resolution of the peripheral manufacturing tool, display proprietorship of processes. A recent textbook
although this is not the case when high resolution on rapid prototyping contains over 50 such acro-
International Materials Reviews 2003 Vol. 48 No. 6
Tay et al. Solid freeform fabrication of ceramics 343
laser heating and multiple layer photocuring rely on

optical de ection of laser light. The laser forming
processes are reviewed from this point of view by
Irving.33
Extrudate deposition and some types of ink-jet
printer make use of stepper motor actuation which,
if associated with feedback, can provide<1 mm reso-
lution. In contrast, continuous ink-jet printers use the
electrostatic de ection of charged droplets to achieve
position control,34 while in drop-on-demand printers
the relation between printhead and substrate is gener-
ally stepper controlled. The ejection of droplets in
drop-on-demand printers is achieved either by piezo-
electric or electromagnetic actuation or by incipient
boiling of ink using miniature heating elements. Thus,
the scope for new solid freeforming hardware is closely
related to methods of image reproduction and hence
to actuation.
Fuster35 considers that there are ve basic layer
2 Classification of solid freeforming processes a manufacturing processes:
by state and b by dimensional order (adapted (i) liquid solidi cation – photosensitive resins are
from Ref. 12) cured by laser or UV (ultraviolet) light, e.g.
stereolithography, solid ground curing
(ii) melt deposition – molten material is depos-
nyms.22 For this reason, a glossary of acronyms is
ited in layers, solidifying as it cools, e.g.
given at the end of this review and it is attempted
throughout the script to employ clearly comprehen- fused deposition modelling, multiphase jet
solidi cation
sible terms with minimal resort to obfuscation.
(iii) powder sintering – powder layers are bonded
using a laser to fuse each layer, e.g. selective
Scope of solid freeforming processes laser sintering
A large number of general reviews of solid freeforming (iv) sheet lamination – sheets (paper, foil) are cut,
processes have emerged over the past decade. These stacked and joined, e.g. laminated object
vary considerably in their scope and their methods manufacturing
of classi cation. Kruth12 concurs with the present (v) indirect printing – powder layers are bonded
authors in recognising the problem of terminology using a binding agent usually sprayed on using
and classi cation and presents two approaches ink-jet technology.
(Fig. 2). In the rst, the processes are organised Fuster chose not to report laser chemical vapour
according to the state of the building materials used; deposition in which the site of reaction is controlled
in the second, organisation is according to the dimen- by local heating provided by a laser de ection system,
sional order of deposition. Kruth invents a new word or to report direct ceramic ink-jet printing.
‘incress’ to describe these technologies in contrast to In each case, the main quality factors in the solid
the present authors who seek etymological re nement freeforming of ceramics that command attention are:
and economy. dimensional control, geometry of vertical walls, sur-
Reviews by Marcus and co-workers13,23 provide a face nish, microstructure, speed and integrity (e.g.
concise list of the principal processes while Kochan’s porosity). Although some of these technologies are
review20 focuses on the computational aspects of still under development, the promise of maturing to
multilayer photopolymerisation. Pham and Gault14 a major multi-billion-dollar worldwide industry is
provide a more exhaustive review based on Kruth’s treated with optimism.16
classi cation.12 Chua’s review22 reports the trade- Solid freeforming was initially successfully demon-
names of individual processes and sometimes this strated for the rapid prototyping of plastic parts14
obscures the recognition of their physical bases. but in rapid prototyping the material performance is
Shishkovsky’s concise review24 focuses on the ability less stringently speci ed than in manufacturing. The
to form functional gradients in solid freeforming, application of solid freeforming to ceramics manufac-
sometimes called ‘second generation solid freeform- turing is motivated by the advances in engineering
ing’. Halloran25 views these processes from the cer- ceramics36 where methods of creating complex shapes
amics perspective. A number of other reviews provide are limited. A particular advantage is the ability to
similar material for diVerent readerships.26–31 Conley create functional gradients both in electroceramic
and Marcus,13 Kruth,12 and Pham and Gault14 have applications and to assist in metal–ceramic joining.
provided excellent comparisons of the diVerent RP Ceramics often incur high machining costs for low
methods available commercially. Qualitative com- production numbers and high tooling costs in injec-
parisons of these methods in a ceramics context have tion moulding of large batches. The use of solid
been reviewed by Wang and Krstic.32 freeforming as a rapid prototyping method enables a
The solid freeforming processes can also be classi- designer to evaluate new ceramic materials and
ed according to the method of actuation and position designs under diVerent test conditions. The wider and
control. Thus, laminated object manufacture, selective more powerful application of solid freeforming is in
3 Schematic representation of stereolithography

(multilayer photopolymerisation) in which
successive layers of photopolymerisable
monomer are cured by UV laser which scans
surface (from Ref. 37. Reprinted with permis-
sion of The American Ceramics Society,
www.ceramics.org. ©1996. All rights reserved) 4 Geometry of cured tracks in stereolithography
(reprinted from Ref. 14, ©1998, with permission
manufacturing itself where it allows the combination from Elsevier)
of complex shape, three-dimensional functional gradi-
ents and individuation in a mass production pathway. oV to leave hydrophilic non-printing areas. The only
Thus, every mass-produced component can be diVer- common feature is photopolymerisation.
ent, for example, as a personalised product or for the Stereolithography is better denoted multilayer
purpose of security and traceability. photopolymerisation and is based on the layered
Among the techniques used for freeform fabrication construction of a polymer or particle- lled polymer
of ceramics are stereolithography,37 fused depos- in a tank of photocurable monomer or oligomer.
ition,38 selective laser sintering,39 laminated object The apparatus is shown schematically in Fig. 3.
manufacturing,40,41 three-dimensional printing,42 Photocurable resins generally contain 2–5% photo-
direct ceramic ink-jet printing,43 and laser chemical initiator that generates free radicals in the presence
vapour deposition.44 There are no rules for process of UV light. The monomer or oligomer is polymerised
selection, but in this review examples of successful when attacked by free radicals but the reaction stops
applications for each process are presented. in the absence of light because free radicals react with
oxygen. The cured depth C is given by49
d
A B
E
Stereolithography C =D ln max . . . . . . . . . (1)
d p E
One of the methods of giving the computer a building c
capability is via the directed movement of a focused where D is the penetration depth of the resin deduced
laser beam. Solid freeforming methods described as from thep Beer–Lambert law, E is the peak value
max
stereolithography, selective laser sintering (SLS), laser of exposure (J mÕ 2) of a laser beam with Gaussian
chemical vapour deposition (LCVD) and the cutting distribution of energy and E is the critical energy
c
density below which polymerisation will not proceed.
stage of laminated object manufacturing (LOM) were
thus made possible. Similarly the cured line width L is given by
w
A B
The term ‘stereolithography’ is slightly confusing. E 1/2
Lithography is a method of printing from a plane L =ã 2W ln max . . . . . . . (2)
w o E
surface and contrasts both with letterpress in which c
the printing areas are raised and intaglio in which where W is the Gaussian half width of the laser
they are recessed.45 The pre x ‘stereo’ denotes three- o
beam. Experiments based on this approach indicate
dimensional quality or solidity but stereolithography the overlap and cure depth needed to produce a fully
does not use lithography and it is not a printing cured model. Figure 4 shows the geometry of cured
process. This is confusing to the student of manufac- tracks. The extent of overlap determines the uniform-
turing processes because lithography itself is a distinct ity of cure depth. Thus, in Fig. 5, the overlap is varied
freeforming process for ceramics46 among a range of from 0 to 50% and a uniformly cured layer of a depth
other printing operations including screen printing,47 of about 400 mm is obtained in the latter case.
transfer (often known as decal) printing,48 and ink- Recently, the need to recoat layers has been
jet (q.v.). The name has come about only because removed by using a focused He–Cd laser (submicro-
stereolithography bears a vague relationship to the metre stereolithography) to achieve exceptional reso-
current method of manufacturing lithographic print- lution and make submicrometre walls. It is a point-
ing plates. These are prepared from porous anodised by-point method that scans a static tank of monomer
aluminium on which a layer of photocurable polymer in all dimensions relying on a monomer with very
has been deposited. The plate is exposed to UV light low absorption coeYcient so that only at the focus
to cure the resin and the unwanted oligomer is washed does the reaction initiate. It is unlikely to be suitable
5 Effect of track overlap on uniformity of cure depth: comparison of experiment and modelling for 0%
(top) and 50% (bottom) overlap (adaptation of figure reprinted from Ref. 49, ©1995, with permission
from Elsevier)
for ceramic suspensions, although it might be applied achieve high density the freeformed body should be
to polymeric ceramic precursors.50 highly lled with typically 50–65 vol.-% solid. The
Where the resin is highly lled with ceramic suspension, on the other hand, must have a relatively
particles (volume fraction 0·1<w<0·5) which have low viscosity. A similar approach is taken by Chartier
similar diameters to the radiation wavelength, C is and co-workers55,56 for producing ceramics using
given by51 d
laser polymerisation of a ceramic paste of up to
A B
60 vol.-% powder based on a UV photocurable
2d: n2 E
C = 0 ln max . . . . . . . . (3) monomer. Thin layers (25 mm) could be achieved
d 3Q Dn2 E and the dimensional resolution was 200 mm. Flexural
c
in which d: is the average particle diameter, Dn2= strengths of alumina parts made in this way are
(n n )2 where n and n are the refractive indices similar to those of conventionally made ceramic.55
p o p o Aluminosilicate parts with 50 vol.-% powder have
of the powder and medium respectively, and Q is the
scattering eYciency term. Experimental values of Q been produced in a similar way.57,58
for alumina powders are 0·13–0·24 and for silica in The three-dimensional part is fabricated by success-
aqueous media 2–4. Thus the cure depth is reduced ive curing of layers of suspension as the focused laser
as noted experimentally.37,52 beam scans the liquid surface to reproduce the inform-
The rst solid freeforming machine to enter the ation in a slice of a three-dimensional computer
commercial market was supplied by 3D Systems in image. The resulting solid ceramic–polymer compos-
1988.12 The method is one of the most widely used ite is built up on an elevator platform, which lowers
in solid freeforming and was described by Kodama the part incrementally into a vat containing the liquid
in 1981.53 It is used to create ceramic parts by in steps of 50–500 mm, which is the eVective layer
polymerising a UV-curable binder lled with ceramic thickness. As the elevator is lowered into the vat,
powder by exposure to UV radiation from a laser37 liquid resin covers the last solidi ed layer. The recoat-
using an arrangement similar to that shown sche- ing and levelling of a new layer of resin then ensures
matically in Fig. 3. While most stereolithographic that the liquid level corresponds to the focal plane
systems employ the forming strategy outlined in and excess resin beyond the desired layer thickness is
Fig. 3, signi cant diVerences in the lasers and in the removed.14 The use of a laser is not the only way to
recoating and beam delivery mechanisms can be photocure the pattern in each layer. Conventional
found.54 Lasers used in current practice are helium photographic masking can be used. A mask can also
cadmium gas lasers, argon ion gas laser and more be based on a liquid crystal display (LCD) on which
recently solid state Nd–YVO lasers.12 the pattern of non-curing regions is updated layer by
In order to make ceramic 4parts, the photopolym- layer.59 Micro stereolithography with a dynamic mask
erised monomer is charged with powder37 and to generator allows the exposure of a single layer in one
a b c
a investment casting core; b investment casting made with core shown in a; c electromagnetic band-gap structure
6 Ceramic structures prepared by stereolithography (courtesy Professor. J. W. Halloran, University of
Michigan, USA)
irradiation60 and this process can use a LCD mask layers has been developed to overcome recoating
by frequency conversion of the image to overcome problems encountered with a scraper blade.12
the opacity of LCD screens in the UV region.61 The method of stereolithography developed by
Scanning with conventional UV light transmitted Chartier and co-workers55,56,64 for ceramics makes
through an optical bre with focusing lens and shutter use of a paste based on acrylic monomers with photo-
has also been used.62 Once a planar resin surface is iniator, dispersant and a thickening agent. The paste
established, the laser draws the part border followed is spread on the building platform by a mechanical
by hatching; lling in the area within the borders. device to give layers of thickness 25 mm or above and,
The process is repeated several times until the part is since it has a high viscosity at low shear rate, no
built. The platform is raised and the solid polymer container walls are needed for the platform.
emerges from the vat. The cured resin serves only as Photocured widths as low as 400 mm were obtained
a binder for ceramic particles and is removed by at low energy densities for zircon which had the
slow heating to 250–500°C, followed by high temper- largest diVerence in refractive index compared to the
ature sintering. Examples of ceramics made by stereo- monomer. For alumina, the mechanical strength was
lithography are shown in Fig. 6. Greco et al.58 used similar to that measured on material prepared by
silicon containing acrylic monomers with yields of compaction.
21–30 wt-%SiO to make aluminosilicate ceramics Stereolithography, like most of the other solid
thus pointing the2 way to a wider application of poly- freeforming methods, can be used to make complex
meric precursors in stereolithography. ceramic parts indirectly by making a polymeric mould
In the micro stereolithography of ceramic suspen- which can be lled with ceramic suspension by low
sions, ner resolution was obtained by adding a UV pressure injection moulding.65–67 Wang et al.68 have
absorber to the organic vehicle to reduce the scat- devised an indirect method in which a concentrated
tering eVect of ceramic particles.63 The absorber had ceramic suspension is vacuum cast into a polymeric
an absorption coeYcient at 364 nm, 1000 times higher mould that is made by stereolithography and can
than the photo-initiator. At 0·3% addition, the reso- have complex geometry and ne surface quality.
lution was 2·6 mm and the experimental results were Indirect stereolithography has been used to make
in agreement with scattering calculations. fugitive epoxy moulds with a core structure of lattice-
Resin recoating is a time consuming step12 and work into which a hydroxyapatite suspension was
may create a ‘trapped volume’ in the part; excess resin cast.69–71 The mould and the organic binder in the
that cannot be drained through the base.14 The pres- suspension were then pyrolysed to leave a complex
ence of trapped volume causes a build up of unwanted but highly ordered pore structure. The sintered mater-
polymerised resin at the surface which may aVect ial was intended for orthopaedic applications in which
accuracy and surface nish. Although many recoating both natural and synthetic foams have traditionally
mechanisms have been invented to eliminate this been used. This approach has the advantage over
problem, e.g. scraper blade, inverted U, viscous reten- ceramic foams because multimodal pore sizes and
tion, positive displacement pump,12 the contact channels are needed for hard tissue scaVolds. Fine
between the recoating mechanism and the liquid pores are ideal for cell development while larger pores
surface remains a problem. This is even more signi - in the >100 mm region are needed for blood vessels.
cant for highly viscous ceramic suspensions where a Ceramic foaming processes do not allow these com-
high shear stress transmitted during coating may plex microstructures to be designed and then built
damage the part under construction. A process in to order.
which the ceramic suspension is prelaminated into Another disadvantage associated with high vis-
semisolid foils and pressed into the previous cured cosity ceramic suspensions is the long time needed to
drain the excess resin from the completed part.

Stereolithography also requires structures to hold the
various connecting parts of the product and support
the weak overhanging regions during the recoating
of layers.12 These require additional material and
time. The optimisation model of Pham et al.72 assists
decisions on part orientation on the platform and
various slicing and hatching strategies have been
devised to reduce time and distortion.73 A model that
predicts the depth of cure as a function of photo-
initiator concentration and intensity can be applied
in stereolithography74 and errors and compensation
methods in stereolithography apparatus have been
described by Pham.75
Extrusion freeforming of ceramics 7 Schematic diagram of fused deposition

The creation of an artefact from a cylindrical strand modelling process (adapted from Ref. 24)
of deformable ceramic has its origin in the Egyptian
Naqada 1 period (4500–4000bc)7 where coiled clay
ent shear rate cb is then related to the true shear rate
at the wall cb bya
pots were produced. The application of computer
control to a movable extrusion head has spawned a t
range of construction methods based on this ancient 8v
idea which are best described under the heading cb =cb +
a t D
‘extrusion freeforming of ceramics’. In fused depos-
ition modelling (FDM),76 a thermoplastic polymer, from which v, the slip velocity, may be deduced from
typically acrylonitrile butadiene styrene is extruded the slope of the apparent shear rate versus reciprocal
through a 0·5–1 mm dia. nozzle using the solid poly- die radius plot on the assumption that the slip velocity
mer strand as the extrusion ram. The technique, as is a unique function of the true wall shear rate.83
shown schematically in Fig. 7, was developed and Related processes include melted extrusion model-
commercialised by Stratasys Inc. (USA) for processing ling84 and multiphase jet solidi cation (MJS).85–87 In
polymer and wax parts.38 Temperature control is to the latter, a ceramic or metal powder suspension in
±0·5 K and dimensional accuracy relies on the use a wax or polymer vehicle is extruded onto the building
of shrinkage compensation factors77 and optimised platform. In fused deposition of ceramics, structural8
deposition.78,79 The same approach, applied to cer- or piezoelectric ceramics are prepared either directly88
amic suspensions in a polymer or wax vehicle, is or indirectly by solid freeforming a disposable mould
known as fused deposition of ceramics (FDC). into which the ceramic slurry is cast.89 Piezoelectric
Fused deposition modelling and fused deposition ceramics and polymer–ceramic composites with func-
of ceramics should be distinguished from the other tional gradients have been prepared in this way for
extrusion freeforming processes in that the lament sensors and actuators.90–92 The ceramic phase can
is fed into the die between rollers as a solid rod. It also be oriented relative to the poling direction in the
follows that stiVness and resistance to buckling direct fused deposition of piezoelectric ceramic–
between the roller and die must be suYcient to allow polymer composites.93 The lament diameter is
the solid part of the lament at the back of the die typically 1·8 mm80 and the method can be extended
to act as a piston.80 Success in making a range of to multiphase materials (FDMM).94 Rectangular
multicomponent transducers depended on the ratio section pillars can be made by the indirect lost-mould
of lament compressive modulus to melt viscosity at process.95 An example of piezoelectric ceramic pillars
the die temperature.81 In order to avoid pressure intended for subsequent incorporation into a polymer
uctuations, the viscosity of the melt must be uniform to make 1–3 ceramic–polymer transducers is shown
and therefore the process requires a well dispersed in Fig. 8. A similar indirect approach involves gelcast-
suspension free from large agglomerates and debris. ing PZT (lead zirconate titanate) suspensions with an
In the molten state, the suspension should have a low acrylamide monomer in FDM-produced moulds to
viscosity at ceramic volume fractions greater than 0·5. make piezoelectric 1–3 composites.96 Photonic band
For a Si N suspension80 the viscosity was about gap structures for GHz frequencies and piezoelectric
100 Pa s 3at 4 100 sÕ 1 with the apparent activation actuators with spiral or bellows geometry can be
energy for ow being strongly dependent on the shear made in this way. Bismuth titanate components with
rate of the experiment. In the case of these results, a preferred grain orientation were made by seeding the
correction for wall slip was negligible but, in general, un red suspension.97 A wide range of complex shaped
the use of very ne capillaries in extrusion freeforming piezoelectric actuators, some with crystallographic
can introduce a wall slip eVect often encountered in texture introduced by aligning anisotropically shaped
ceramic suspensions. For example, in suspensions grains in the ow direction, have been made by
containing whiskers, slip could account for 50% of FDC.98 In particular, needle-like lead metaniobate
the total ow.82 The usual method to assess wall slip crystals with aspect ratios of 7 produced a piezo-
in rheometry is to use a series of dies of diVerent electric gure of merit 70% higher than the pressed
diameter D, but with the same L /D ratios. The appar- material.
9 Control of filament diameter using adjustable

a nozzle in extrusion freeforming (from Ref. 105)
family of processes is novel and is to be distinguished

from solidi cation by phase change or evaporation.
Ideally in these processes, a range of nozzle dia-
meters is preferred104 so that large nozzles can be
used to ll bulk, while ne nozzles are brought into
play for detail. Tseng and Tanaka105 have approached
this problem with a variable diameter nozzle that can
provide a range of extrudate diameters from a single
adjustable ori ce (Fig. 9). They also describe a planar
adjustable nozzle that deposits layers of diVerent
width from a pressurised chamber. The extrudate can
be drawn oV by a roller, which also helps weld it to
the previous layer. Bonding to the previous layer has
a strong in uence on the nal component strength
and can be related to the forming parameters.84
b Fused deposition of ceramics has been applied to
the fabrication of functional ceramic parts and Fig. 10
8 Piezoelectric ceramics made by fused shows a range of electroceramic transducers made in
deposition of ceramics (FDC): wax mould
(shown in a, where scale bar represents 1 mm)
this way. The starting materials for FDC are laments
is used to make fine ceramic pillars (shown in of ceramic powder mixed with thermoplastic polymer
b, where scale bar represents 100 mm) for or wax binder. The laments are manufactured in
ceramic–polymer composite transducers (from ways similar to those used by the ceramic injection
Ref. 95) moulding industry. The starting materials are mixed
by high shear, dispersive mixing methods designed to
break up agglomerates and distribute the ultimate
These methods can also be used to make fugitive particles throughout the continuous phase. The mix-
moulds consisting of latticework that can sub- ture is granulated and extruded to produce contin-
sequently be in ltrated with ceramic slurry. When the uous lengths of exible lament typically of 0·5–2 mm
ceramic is red, a controlled ordered architecture of nominal diameter.106 SuYcient strength is needed for
porosity remains for applications in lightweight struc- it to be fed into a movable head. In the heated nozzle
tures, molten metal lters, catalyst supports and bone it softens to just above its melting point at the exit.
grafts.99 Applied to the direct formation of latticework The lament is then deposited by raster motion
structures, this use of extrusion freeforming avoids according to the patterns de ned by the CAD model.
the ‘staircasing’ eVect of surface roughness that pre- Layer building starts by de ning the boundaries
vails when monolithic objects are created.100,101 followed by raster motion of the nozzle head
Extrusion freeforming102 is the term that best depositing material inside these boundaries as a series
embraces all these techniques but it is presently used of adjacent streams. Each stream is deposited on top
speci cally for extrusion of monomer to produce, of, or next to, its predecessors and bonds by contact
typically, Nylon 6 on a heated platform by extrusion fusion. The molten lament solidi es rapidly upon
through a 250 mm dia. nozzle. This method too can deposition by natural cooling. The lament is laid
be used for ceramic prototyping. Perhaps this could layer upon layer, and a three-dimensional object
be designated reaction extrusion freeforming. A capro- resembling the model is built and then subjected to
lactam was deposited at 70°C onto a hot plate held binder removal and sintering to produce a dense
at 165°C. Gelation occurred quickly to provide shape ceramic component.
retention while complete polymerisation took A signi cant advantage of FDC is that it is not
longer.103 This method of state change in the extrusion demanding upon equipment; it uses a low viscosity
a tube array; b bellows; c spiral; d curved transducer; e telescoping; f radial actuators

10 Electroceramic transducers created by FDC (reprinted from Ref. 97, ©2001, with permission from
Elsevier)
feedstock that can be readily dispensed using low ive cooling of previously deposited adjacent streams.
pressures (<0·7 MPa).17 There is very little material Incomplete lling occurs as the nozzle turns around.
waste during or after production of the model.14 The lament traces a curved tool path instead of the
There are generally no concerns about operator expo- sharp turn de ned in the CAD model. Consequently,
sure to toxic materials or lasers. Little cleaning is voids can be found within the part. The use of more
needed and the materials can be changed quickly. intelligent tool path generation software, build stra-
Because the material solidi es quite rapidly after it tegies and machine control software have helped to
leaves the nozzle, it is possible to form short over- improve part quality and accuracy.12 As the resolution
hanging features without the need for supports of the process is dictated by the lament thickness,
although, in general, they are used. A dual tip mechan- another drawback of FDC is its inferior surface nish
ism can be used to dispense two materials – a primary compared with parts produced using other solid
material for modelling and a secondary material for freeforming techniques such as stereolithography.38
producing a support structure. Subsequent nishing operations are needed for
In another version of extrusion freeforming, evapor- improvement of the surface.111 One approach to the
ation of water from the suspension is used as the amelioration of surface ripples is to incorporate a
method of changing state after extrusion rather than blade that trowels the freshly deposited extrudate,
solidi cation107,108 and this method, developed at which is described as ‘contour crafting’.112
Sandia National Laboratories, USA has been named Fused deposition of ceramics has been demon-
‘robocasting’. Suspensions of 50–65 vol.-% ceramic strated for Si N ,113 fused SiO , Al O and
powder in water with less than 1% dispersant and PZT.111,114 The 3 prototyping
4 2
of investment2 casting
3
having a viscosity typically of 50 Pa s at 1·7 sÕ 1 are positives is a major application.38 Extrusion freeform-
extruded through a nozzle onto a building platform ing, which uses two extruders to dispense dissimilar
heated to 40–60°C. Initial drying provides suYcient materials into a small mixing head, has been employed
increase in ceramic volume fraction to give a yield to prototype functionally graded material.111 The
stress that prevents deformation. State change can same technique has been used to extrude alumina in
also be eVected by evaporation of non-aqueous sol- an aqueous polyvinyl alcohol suspension using two
vents and this is the method used to make metal extruders supplying a mixing head with suspension
matrix composites with silicon carbide powder (up to and crosslinking agent.115 A melt extrusion freeform-
20 vol.-%) or whisker reinforcement109 using a poly- ing process known as ‘multiphase jet solidi cation’
methylmethacrylate (PMMA) binder in dioxane and (MJS) has been developed by the German Fraunhofer
extruding through an 840 mm needle with stepper Institutes IFAM and IPA for the fabrication of both
driven syringe. Fused deposition modelling of pastes metal and ceramic (SiC) near net shape parts for
can also be applied to semisolid metals in which the functional applications.116
volume fraction of solids is determined by the lever Another member of the extrusion freeforming
rule between the solidus and liquidus and thus con- family that has recently emerged is ‘direct write
trolled by temperature.110 fabrication’. The inks are solvent based and closely
Internal defects are a concern when this technology related to screen printing inks. Direct write with a
is used to fabricate structural ceramic components.38 positive displacement pumped ink and plotter
These defects usually arise from debonding or poor system117,118 has been used for ceramic processing
bonding between adjacent streams or adjacent layers, and bears a formal similarity to extrusion freeforming
or incomplete lling in the part.106 Their causes are in that a suspension of ceramic particles with ceramic
inconsistent material ow due to variation in lament volume fraction 0·3–0·35 and viscosity in the region
diameter, lament slippage between rollers or excess- 1·5 Pa s is extruded through a nozzle to produce a
11 Schematic diagram of selective laser melting

process (adapted from Ref. 54)
pattern on the substrate. It has been used to create

resistors, microwave components and thermal print-
heads. It allows multiple layers with a constant cross-
sectional area to be deposited on uneven surfaces.
The extruded uids can be self-levelling so it can be
used for a range of ceramic pastes for ZnO varistors 12 Titanium alloy nozzle made by selective laser
and capacitor dielectrics.119,120 sintering (SLS) showing sharpness of grooves
and surface finish (reprinted from Ref. 123,
©1999, with permission from Elsevier)
Selective laser sintering
Selective laser sintering (SLS) originated at the
University of Texas at Austin in 1986 and was com- form lowers the part and the next layer of powder is
mercialised in 1992.17 A wide range of laser sintering deposited. When the shape is completely built, the
machines has been developed subsequently.12 It has nished part, buried within a cake of loose powder,
been used for metals, ceramics121 and polymers.122 A is separated from the loose particles which may
thin layer of powder is spread out and levelled over sometimes be recycled. The build time can be pre-
the top surface of the building platform, as shown in dicted and there are strategies to minimise it.127
Fig. 11. A laser then selectively scans this layer to Parts processed by SLS are often porous and post-
fuse the forming areas as de ned by the geometry of processing is necessary when strength is required in
the cross-section of a CAD model and to leave the ceramic parts.17 Conventional sintering and hot iso-
non-forming areas as supports for subsequent build- static pressing are two common methods used to
ing. Although the process is described as sintering, in increase nal density.
many polymer and metal SLS processes complete No support structure is needed as the non-fused
fusion occurs and the expression ‘selective laser melt- powder remains in place to act as a support itself.
ing’ is more appropriate. The laser energy also fuses Changing from one material to another is simpler
consecutive layers together. The building chamber is than in many of the liquid based solid freeforming
purged with inert gas and is often heated to raise the techniques, given the dry solid nature of the starting
temperature of the uppermost layers of powder. This material.
reduces the additional laser energy required to heat Selective laser sintering can process powders
the powder to its fusion temperature during fabri- directly without the use of a sacri cial binder,128
cation and may help to reduce residual stress develop- unlike other solid freeforming methods which demand
ment and to relieve stresses that have been established. speci c materials such as photopolymers in stereo-
The titanium alloy nozzle shown in Fig. 12 indicates lithography. In indirect SLS, on the other hand, low
the quality of detail and surface nish that can be temperature fusion of a binder is used to assemble
achieved in SLS.123 the powder and subsequent pyrolysis and sintering
Powder can be delivered into the moving laser steps are needed. This can be an organic polymer
target by dry powder ow (which may be gas assisted), coating129 or a low melting inorganic salt.130 The
selectively by ink-jet printing or by metering and coating of metal or ceramic particles with a polymeric
dispensing of dry powder. A method of dry powder binder can be achieved by uidised bed methods.131
dispensing that has its origins in the sand painting of The reason for the indirect approach is that laser
the Navajo North American Indians has been sug- sintering of high melting point ceramics requires a
gested124 and could provide a route to functionally high level of laser energy and can create large thermal
graded materials.125,126 The quest now is for combined gradients, thermal shock and hence diYculty in form-
shape and compositional control that will pave the ing a contiguous shape.39 This is partially overcome
way for the SLS of three-dimensional functional gradi- by incorporating a second phase binder of lower
ents. After each layer is deposited, an elevator plat- melting point into the ceramic powder. This second
14 Schematic diagram of laminated object

manufacturing (LOM) process (adaptation of
13 Temperature fluctuations during SLS: figure reproduced from Ref. 13 with permission
temperature–time trace with thermocouple of ASME, ©1997)
location in open box sample shown inset
(adaptation of figure reprinted from Ref. 138, due to particle neck growth and melting resulting in
©1999, with permission from Elsevier) local densi cation and particle movement.139 A model
for pulsed near infrared radiation from a Nd–YAG
laser shows that pulsed mode uses lower average
phase can be an organic binder coated on the powder, power and lower average temperature and therefore
an inorganic binder (e.g. ammonium dihydrogen produces reduced residual stresses.140
phosphate)132 or a metallic binder.128 Methacrylate Numerous methods have been employed to increase
polymers have been synthesised to act as organic the powder bed density in order to increase the
binders.129 Nelson and co-workers133,134 provide a ceramic or metallic part density without sacri c-
model of the SLS process that predicts the sintering ing freeforming capability. Conventional means of
depth for SiC, PMMA and SiC powder coated with improving the powder bed density include the use
PMMA. A post-SLS process is then needed. Volpato of spherical particles, bimodal size distributions of
et al.135 sensibly preferred the term ‘indirect selective powder, agglomeration of ne powder and optimising
laser sintering’ to describe the low temperature joining the volume fraction of combustible binder.17 Another
of particles with a binder in their attempts to form approach is to increase the eVectiveness of the powder
complex parts with overhangs. The term ‘direct metal distribution process in SLS by the use of electrostatic
laser sintering’ is reserved for the selective melting of elds,141 magnetic elds142 or mechanical agitation of
powder using high laser intensity.136 the powder and/or powder bed.143 On the other hand,
Organic binders need to be removed before sinter- in some applications, e.g. ceramic moulds or leachable
ing, while inorganic binders may leave a second phase. cores for metal casting, porosity in the part is an
In the case where a metallic binder, often aluminium, important function and SLS processing of these parts
is used, a post-SLS process is required to oxidise the allows direct fabrication.
aluminium to alumina. The extent of conversion and Laser sintering of zircon sand (ZrSiO ) and silica
hence the strength of the part is dependent upon the 4
sand (SiO ) have been employed in industry, while
laser energy.39 2
research with ZrSi, ZrSiO , SiC, graphite and other
Each material requires diVerent heating and laser types of ceramic continues.122 Composites such as
parameters.14 Process maps have been devised to SiC/Al or Al O /Al can be made by selective laser
predict thermal gradients and residual stresses.137 2 3
reaction sintering.132 The application of SLS to mix-
Temperature cycles and thermal gradients in a laser tures of Cu–Ti–Ni–C powders leads to TiC metal
melted thin wall enclosure have been measured with matrix composites prepared in situ, potentially with
embedded thermocouples and high speed imaging complex and novel microstructures.144
with a digital infrared camera.138 An example of the
temperature uctuation is shown in Fig. 13. The
corresponding residual stresses were estimated by a Laminated object manufacturing
hole drilling method using laser interferometry to Laminated objected manufacturing (LOM), as shown
measure strain. Maximum local residual stresses in schematically in Fig. 14, was developed in 1985 and
the region of 300 MPa were reported. Parts require commercialised by Helisys Corporation in the USA
slow cooling in the machine before they can be to build components with layers of paper or plastic.12
removed for post-processing. Recycled powders must The sheets are laser cut according to a pattern de ned
be sieved to remove agglomerates, which interfere by CAD and laminated with adhesive to the previous
with the smooth application of the next level of layer. The laser also dices, or cubes, the excess material
powder. to help with extraction of the nished component.
Models for the temperature eld in SLS are needed The waste material is left in place during construction
to plan the scanning process. They must take into to serve as a support. The process is repeated until
account the changes in thermal transfer properties the component is formed.
15 Early examples of alumina components made

by LOM (from Ref. 18. Reprinted with
permission of The American Ceramics Society,
www.ceramics.org. ©1994. All rights reserved) 16 Zirconia–alumina laminates made by LOM
(from Ref. 40. Reprinted with permission of The
American Ceramics Society, www.ceramics.
The process has been modi ed to fabricate ceramic org. ©1996. All rights reserved)
components.36,145 Instead of paper, thin (~100 mm)
ceramic tape, which is pre-processed by mixing cer-
amic powder with an appropriate binder by tape of Al O /Ce–ZrO ).40 An example of the micro-
casting, roll compaction or extrusion, is used. After 2 3 of such 2 laminates is shown in Fig. 16.
structure
the sheets have been stacked to assemble a physical Similarly, functional gradients of TiC–Ni have been
three-dimensional model of the original CAD descrip- made by LOM followed by combustion synthesis.150
tion, the part is removed from the platform and the In LOM, the part remains embedded within a
waste material is separated manually. The part is then block of supporting material that is diced and broken
subjected to binder removal followed by sintering. As into chunks before removal. Because the surfaces
lamination occurs under applied pressure, one con- adhere to one another, cleaning is a manual process151
cern is the relaxation of residual stresses causing and much care is needed, as the scrap is as strong as
delamination and bloating during binder burnout. the part. The amount of scrap generated is large and
Pressure can be applied during pyrolysis to counteract is not directly recyclable. Making hollow parts is also
this.146 Recent binder removal studies have resulted problematic due to the diYculty in removing the
in a model which allows the estimation of binder in core.14 This diYculty also extends to narrow passages,
an alumina body made by LOM.147 Zhang et al.148 internal cavities with restricted access, blind holes,
describe the roll forming of 700 mm alumina tape etc. The waste chunks must be tiny enough to be
followed by lamination, binder removal and press- manipulated through the small openings. The shear
ureless sintering. The diYculties with ceramic LOM strength of the part is aVected adversely by poor
are also debated by Kochan and Himmer.149 Early adhesion between layers during lamination.152
examples of alumina ceramics made by LOM18 are CerLOM, a modi cation developed by Lone Peak
shown in Fig. 15. Engineering Inc., USA, has been used to combine
In one sense, in contrast to most solid freeforming tapes of diVerent ceramic materials to fabricate multi-
processes, LOM is partly a subtractive method layered composites with alternating composition.40
because it traces the outlines of the parts and discards Another LOM modi cation, the CAM–LEM process,
waste during layer fabrication.41 This makes it poten- was developed at Case Western Reserve University,
tially the fastest technology for building parts with a USA.41 This technology adopts a ‘cut-then-stack’
high ratio of volume to surface area.14 Because the approach where the layer is cut to shape prior to
processing of the sheet can be completely separated placement onto the stack to be laminated. Therefore,
from component building, microstructural defects it is possible to cut arbitrary angles by inclining the
within each layer can be minimised,41 although the laser relative to the sheet to produce bevelled edges
interfaces between layers provide a unique set of at the contour. This avoids ‘staircasing’ in the stack
defects. Shrinkage or thickness variation during part direction. Furthermore, layers of un red and fugitive
fabrication can be compensated as the thickness of tapes can be added to the partially complete stack
the sheet materials is known beforehand36 and thus instead of being built onto it. The fugitive tapes are
LOM has the potential of yielding a highly accurate organic materials that can be removed by thermolysis
part. later. There is thus no need to remove waste material
Another advantage of LOM is that tapes of two manually after assembly, and hollow components can
or more types of material with diVerent properties be constructed. In both of these modi cations, the
can be added to diVerent regions, paving the way for green part must be subjected to binder removal and
fabricating functionally graded materials or multi- sintered. Zirconia, Al O and SiC components have
2 3
layered composites with alternating compositions (e.g. been prepared by the CAM–LEM process.36,153
Research on the use of a non-planar LOM process

has also been carried out to build curved layer parts
to overcome the restriction of at layers.146 This
concept has been implemented with SiC/SiC tapes to
fabricate ceramic matrix composites for aircraft
engine components.
Laser chemical vapour deposition

Preparation of ceramics from vapour phase reactants
on heated substrates by chemical vapour deposition
provides an established method of making ceramic
coatings or thin free standing layers. If laser heating
is used and the beam is moved parallel to the substrate
some control of coating geometry accrues but more
interestingly if the beam be moved perpendicular to 17 Alumina network made directly from vapour
the substrate then a thin rod can be drawn out into phase (reproduced from Ref. 44, ©1994, with
free space and, if the substrate orientation with respect permission from Elsevier)
to the beam is adjusted, complex network structures
can be produced.154–156 Two overlapping beams with
3 mm dia. spots are used. Three-dimensional printing
Alumina and aluminium have been produced from Three-dimensional printing (3DP) was developed at
trimethylamine alane with or without oxygen, respect- Massachusetts Institute of Technology, USA in 1992
ively. The method is successful if the reaction product as a method to create preforms from powdered metals
is strongly optically absorbing. The laser power can and ceramics.164,165 It has been used to produce
be automatically modulated in response to the growth ceramic cores and shells for casting applications under
rate to produce a range of geometrical shapes of the name ‘direct shell production casting’ (DSPC)
carbon, iron, nickel and Ni–Fe alloys.157 Laser chemi- invented by Soligen Corporation.166
cal vapour deposition oVers high purity, solid free- In 3DP, as shown in Fig. 18, dry powder is levelled
formed products; boron bres of 20 mm dia. had by a roller to provide a thin layer, typically of 170 mm
tensile strengths of 7 GPa.158 The growth rate using thickness. As an alternative to the roller, mechanical,
low pressure chambers is in the region of 100 mm sÕ 1, acoustic or ultrasonic vibration can be used to con-
but with pressures over 1 atm, rates of several mm sÕ 1 solidate the powder bed.167 An ink-jet printhead then
are possible.158 Fibres of diameter 20 mm can be moves across the powder in raster motion and prints
produced in the form of microsprings using high a layer of binder selectively onto the loose powder as
strength bres such as boron. The ne mesh structure de ned by the CAD model. In early work on metal
shown in Fig. 17 is alumina made directly from the powders (316 stainless steel, 15–30 mm dia.) the
vapour phase.44 spraying of binder cut a trench through the powder
The method is well suited to the production of high bed and redistributed the powder. This was solved
temperature thermocouples of SiC/C in the form of by pretreating the metal powder with 0·05% salt and
built-in sensors in ceramics or ceramic composites.159 moistening the powder bed to increase its cohesive
Thus silicon is obtained from tetramethylsilane strength.168 As the binder diVuses through the powder
(TMS), carbon from the decomposition of acetylene by capillary action, neighbouring particles are pulled
and the insulating layer of Si N from a TMS and together by surface tension eVects.165 The layer print-
3 4
ammonia mixture. The target temperature is about ing process is repeated and parts are built in a
700°C. A similar method can be used to in ltrate container which is tted with a piston to lower the
layers of powder from the vapour phase.160 A recent part incrementally into it. On completion it is oven
general review of LCVD discusses the preparation of cured and excess dry powder is removed before
complex shapes from metals, carbon, ceramics and sintering. Figure 19 shows a complex surface-textured
semiconductors.161 toroid made by 3DP. Figure 20 shows the detail that
These gas precursor methods have come to be can be achieved in solid freeforming and the internal
known as ‘selective area laser deposition’ (SALD)162 architecture that is possible.
and ‘selective area layer deposition vapour in ltration’ As in SLS, overhanging features are supported by
(SALDVI).163 In SALD, shape is built from the solid the free powder. Three-dimensional printing does not
decomposition products of the gas precursor, either require high energy, does not involve lasers or any
pyrolytically or photolytically according to the pat- toxic materials and is relatively cheap and fast.169
tern de ned by the scanning laser. In SALDVI, the The process can be adapted to suit a variety of
parts are formed by selectively in ltrating the powder powders and to generate the desired pore size and
by vapour. Although still in their early stages, shape. By using multiple printheads, additives may
approaches using gas precursors look promising be deposited in a prescribed fashion to create gradi-
because of their capability to produce high temper- ents in composition, e.g. in the fabrication of compos-
ature structural materials, which are beyond current itionally graded zirconia toughened alumina (ZTA)
solid freeforming processes and diYcult to process by ceramic multilayers.170 The through thickness vari-
traditional methods.13 ation in the ratio of tetragonal to monoclinic zirconia
18 Schematic diagram of three-dimensional printing (3DP) method (reproduced from Ref. 164 with
permission of ASME, ©1992)
was attained by varying the yttria content by addition When aqueous polyacrylic acid solution
of the nitrate through a second nozzle. The resolu- (1·4 vol.-%) is printed onto a porous ceramic powder
tion in gradient was 105 mm before sintering. bed, the solution permeates to diVerent extents in
Compositional control at a resolution of 100 mm is diVerent powders to produce a coherent assembly of
possible.177 particles.175 The droplet also spreads, widening the
The technology was developed initially to produce adhesively bonded track, and the sessile drop radius
ceramic moulds for metal castings directly and, r follows the relationship
although the nal parts may be porous, they are
r=a(b+t)n
suYciently strong for the intended applications. With
proper placement of droplets, printed parts with where t is time and a and b are constants with
controlled surface texture and internal microstructure n # 0·2.176 Polymer molecular weight should be less
may be created. This method has been used to make than 15 000 to ensure adequate permeation.177
casting moulds with tailored surface texture for ortho- The next stage is to remove the non-forming
paedic implants that encourage bone in-growth.172 powder by immersion in a liquid, usually water,178
However, fabrication of structural ceramic parts using without damage to the forming areas. Redispersion
this process was more challenging. Although the use
of ne powder improved sintering of the 3DP parts,
its high surface area decreased the powder owability
and therefore it became diYcult to obtain layers of
defect free powder. Several methods have been
implemented to produce dense ceramic parts with
ne powder by intermediate isopressing or by mod-
ifying the binder or powders.42
The process was considerably re ned by direct ink-
jet printing (q.v.) the layers of the powder bed, in the
form of an aqueous suspension with additives such
as dispersant and low molecular mass polyethylene
glycol, onto a porous support.173 This overcomes the
microstructural inhomogeneities known to charac-
terise compacted dry powders.174 Direct printing
means the powder can be well dispersed in a liquid,
agglomeration is not needed for uidity as it is with
ne, dry powders and a uniform arrangement of well
dispersed particles can be formed on a porous sub-
strate which acts to remove the medium as in slip
casting. The binder solution can then be indirectly 19 Complex surface textured shape made by
ink-jet printed onto the dried layer to give the form- 3DP (reprinted from Ref. 171, ©1999, with
ing areas. permission from Elsevier)

been made by spraying glassy carbon particles pre-

treated with a catalyst and in a solution of furfuryal
resin, prior to pyrolysis and treatment in a silicon
melt.181
Indirect ceramic ink-jet printing has also been used
to make an injection moulding tool with conformal
cooling channels.182 The shape was made in stainless
steel powder, sintered and in ltrated with copper by
a capillary method. This tool did not show temper-
ature variations in a moulding run, thus ensuring
better consistency in moulding dimensions.
Multilayer printing in general is positioned to play
an increasing role in manufacturing. It was previously
a con ned to capacitor and multilayer ceramic device
production which relied on screen printing, a stencil
method of building up a three-dimensional object.
The success of 3DP, the emergence of direct ink-jet
printing and the ‘direct write’ methods mean that a
wider taxonomy of inter-industry manufacturing pro-
cesses is needed in order to take advantage of the
possibilities that now exist.183 The ‘direct writing’
processes using pressured ink reservoirs117–120 are
formally related to extrusion yet they are also three-
dimensional, or multilayer, printing processes.
Similarly, oVset lithography, along with most other
printing processes, can be adapted to solid freeform-
ing46 and used to make multiple layer ceramics based
b on the well established lithographic printing of
20 a Model of Hagia Sophia (Istanbul) produced circuits.184–186
by 3DP and b internal architecture of porous
ceramic filter (courtesy Professor M. J. Cima,
MIT, USA)
Direct ceramic ink-jet printing
Direct ceramic ink-jet printing (DCIJP)187 makes use
of ink-jet printers to create components by multilayer
is enhanced by the back pressure of compressed air printing of ceramic powder that has been well dis-
as the liquid penetrates the porous assembly and by persed in a colloidal suspension. Unlike 3DP, the
the presence of adsorbed organic additives at particle ceramic powder is dispensed directly through the
junctions which weaken interparticle forces. An opti- nozzle instead of just the binder. This process has
mum pH for each powder suspension was needed for the potential to produce a wide range of ne ceramic
best redispersion in order to reduce the slight dissolu- contours with high resolution enabling miniature
tion of ne ceramic powders, in this case silicon components to be manufactured.188 It allows func-
nitride, that can occur in aqueous suspension. Such tional gradients189 that are eVectively stepless in the
dissolved matter can establish solid bridges on drying direction perpendicular to the printing plane to be
that are notoriously diYcult to break. produced by ink blending and dilution. Gradients
Dimensional control of the part is determined both can potentially be made in three dimensions so that
by the accuracy of drop placement within the plane both the shape and the composition of an object can
of printing and by the vertical position of the powder be downloaded from the computer. Direct ceramic
layer.164 Owing to the compressibility of the powder, ink-jet printing relies on suspension preparation by
loads applied from above cause the thin layer of colloidal processing so that particles are well dis-
powder to be displaced downward from its original persed. Thus, agglomerates, often identi ed as the
position and therefore a loss of vertical dimensional source of critical defects in ceramics,174 are either
control can occur. Layer displacements are most removed by ltration or cause the nozzle to block
severe in the middle regions of powder beds. Using a rather than being deposited into the workpiece thus
higher packing density in the powder bed reduces providing fail-safe operation.
compressibility and therefore helps to minimise layer Ink from a reservoir is converted into droplets, and
displacement, but then additional pre-processing propelled through the air to the substrate, which does
work is necessary.179 The raster scanned by the print- not have to be smooth or at. The printing equipment
head on each layer can lead to a ‘stairstepping’ eVect is described in several reviews.34,190 The distinguishing
that appears on the surfaces.13 Surface nish is also features of reprographic ink-jet printing are:191,192
in uenced by the interaction of the binder with the high speed, silent non-impact operation, electrical
powder. computer control, no post-printing treatment, multi-
This technique has also been applied to metal ink capability and the capacity for rapid change
powders for the manufacture of metal tooling.180 As of image.
well as assembly of powders for conventional sinter- Aside from the well established reprographic appli-
ing, reaction sintered silicon carbide components have cations of home and oYce printing, ink-jet printing
21 Schematic diagrams of continuous ink-jet printers a using binary deflection and b based on Sweet’s
principle, using multiple or analogue deflection (adaptation of figure from Ref. 192. Reprinted with
permission of IS&T: The Society for Imaging Science and Technology, sole copyright owners of The
Journal of Imaging Science and Technology)
technologies have also penetrated the emerging mar- Rayleigh205 showed that for droplet formation in a
kets of rapid prototyping and medical imaging,193 non-viscous liquid jet, the oscillations leading to the
high speed titration,194 mass spectrometry sam- break-up of the cylindrical stream into droplets are
pling,195 combinatorial chemistry196,197 and tissue maximum at a wavelength l=4·51d (where d is the
engineering.198 Other applications of ink-jet printing diameter of the jet). Weber206 includedj j
viscosity in
include printing of hybrid microcircuits,199 metallis- the calculation and arrived at a similar result.
ation of the grid patterns of solar cells200 and depos- The ligaments between droplets just before
ition of patterned luminescent doped-polymer break-up can themselves form ‘satellite’ droplets that
lms.201 Ceramic sol–gel inks have been jet printed can either merge with a neighbouring droplet or
to decorate ceramic articles202 and patterns of cer- deposit separately. Satellites can cause misplaced print
amic203 and carbon nanotubes204 have been simi- marks;207 indeed, printers have been built to deposit
larly printed. only satellites and thus re ne the resolution.
A brief account of the recent development of ink- A charging electrode surrounds the jet at the point
jet printing is given by Le.192 There are two main where the droplets separate from the liquid stream.
types of printer: continuous and drop-on-demand The applied voltage determines the landing desti-
(DoD) and their features have been compared by nation of the droplet. When the droplet breaks oV
Edirisinghe.43 from the jet, a charge Q is isolated on the droplet
which, for a given charging voltage V, is given by191
Types of printer
2pe V l
A continuous ink-jet printer forms a stream of drop- Q= o . . . . . . . . . (4)
ln{4d (pd )Õ 1}
lets even when there is no print demand. Droplets c j
are charged and de ected to their destination in an where d is the width of the slot in the charging
electric eld and those not required are collected or c
electrode and e is the permittivity of free space.
recirculated. o
The voltage of the electrode is limited to a few
In the Sweet method,34 developed in the 1960s
hundred volts. When the voltage is too high the
(Fig. 21), an electrically conducting ink is delivered
droplets undergo secondary atomisation if charge
from a pressurised reservoir through a 30–200 mm
repulsion exceeds the surface tension of the liquid.190
dia. nozzle. Just before the nozzle, a piezoelectric
The maximum charge Q is given by205
actuator superimposes a modulated pressure and, on max
leaving the nozzle, the stream breaks up at a matching Q =(64p2e r3c)1/2 . . . . . . . . . (5)
frequency into a continuous series of equidistant, max o
equal sized droplets. The break-up reduces the liquid where r is the droplet radius and c is the surface
surface area.205 Droplet radius would be variable tension of the ink.
without the superimposed pressure wave but, by After leaving the charging electrode, the droplets
perturbing the jet at a xed frequency close to the pass between two de ection plates at a constant
spontaneous droplet formation rate, the droplet for- potential of 3–18 kV. The charged droplets are
mation process is synchronised with the forced de ected in proportion to the charge carried while
vibration, and ink droplets of uniform mass are uncharged droplets are collected by a gutter and
ejected. recycled into the ink reservoir where adjustment for
solvent loss is made before recirculation to the

printhead.
The de ection x of a single droplet is191
A B
QEZ2 2Z +Z
x= d g d . . . . . . . . (6)
2mv2 Z
d
where E is the de ection eld strength, m is the
droplet mass, Q is the droplet charge, v is the droplet
velocity in the direction of the jet, Z is the length of
d
the de ector plates and Z is the distance between
g
the bottom of the de ector plates and the substrate.
In fact, a large number of droplets in close proximity
experience a repulsion force from neighbouring
charges as well as aerodynamic drag.208
The continuous ink-jet printer can be a binary or
multiple de ection system (Fig. 21). In a binary
de ection system, the droplets are either charged or
uncharged. The former transfer to the substrate and
the latter are de ected into a gutter for recirculation.
Elmjet, Scitex and Image are developing printers in
this range.192 In a multiple de ection system, charged
droplets are de ected by diVerent amounts and
uncharged droplets are recirculated. This approach
allows a single nozzle to print a small image swath
and these printers are being developed by Videojet,
Diconix, Domino Amjet and Linx192 and are utilised
in DCIJP. Continuous printers have superior print-
ing speed and can be used at a printhead-to-paper
distance of 25–50 mm but tend to have a higher
capital cost.
22 Schematic diagram of piezoelectric drop-on-
The drop-on-demand (DoD), or impulse ink-jet demand ink-jet printer (from Ref. 190)
system, is the most common reprographic jet printing
method, developed to circumvent the limitations of
continuous jet printing technology, such as start-up the geometrical parameters of the printhead and the
and shut-down requirements, complex charging and physical properties of the ink.190
the need for ink recirculation. It provides systems In general, DoD systems use nozzle openings rang-
well known for their simplicity209 of which there are ing from 20–100 mm, and for thermal DoD an upper
three main types: piezoelectric, thermal and electro- limit of droplet production rate of about 12 kHz is
magnetic. The rst two methods are the most com- suggested.192 Compared with the continuous ink-jet
monly used at present.192 method, DoD devices are less useful for printing on
In the piezoelectric DoD ink-jet method (Fig. 22), curved surfaces or where the ink droplet must traverse
part of the chamber consists of a piezoelectric element, a long distance.
usually a polycrystalline ceramic, which propagates Most of the diVerent types of commercially avail-
an acoustic pressure wave towards the nozzle when able jet printer have been used successfully for DCIJP
excited by an electrical signal. By overcoming the with minor modi cation. The continuous printers
inertial and viscous pressure loss and the pressure include the Biodot jet printer187,210–212 deliberately
associated with the surface tension in the ink menis- modi ed for experimental operation in antibody
cus, an ink droplet is formed at the nozzle and research and hence having low internal volumes. A
expelled. Droplets are ejected only when needed for Domino continuous jet printer213 and a Linx214
printing and no ink recirculation pumps or gas press- printer have also been used for ceramic deposition.
ure sources for the ink are needed; it requires less Drop-on-demand printers have been used for a
hardware than a continuous ink-jet printer.209 wide range of unusual uids and have remarkable
The thermal ink-jet uses a disposable ink-jet print- versatility outside reprography. An IBM four nozzle
head, which contains ink reservoirs, electrical heating ‘colorjet’ DoD printer, the rst used for ceramic
elements and the nozzle plate. A droplet of ink is freeforming,215,216 has also constructed a one-dimen-
propelled from the nozzle when electrical heating sional ZrO –Al O functionally graded material189
causes a bubble of vapour to be formed by incipient for which the2 measured
2 3 composition closely followed
boiling of the ink (Fig. 23). The bubble collapses and the expected gradient (Fig. 24). Other applications of
capillary forces draw ink from the reservoir for the DoD printers include refractive lens fabrication with
process to begin again. The dimensional stability, hybrid organic–inorganic materials,217 deposition of
accuracy and uniformity of the ori ce as well as the zirconia from aqueous suspension218 and deposition
ring signal pro le in uence jet performance (droplet of PZT powder.219 An electromagnetic jet printer
frequency, volume and velocity) signi cantly.192 The provides a robust device for studies of droplet depos-
mass and velocity of the droplet are also functions of ition and ink development220 and such printers have
23 Operating principle of thermal ink-jet printer (from Ref. 192. Reprinted with permission of IS&T: The
Society for Imaging Science and Technology, sole copyright owners of The Journal of Imaging
Science and Technology)
been used to deposit superconducting tracks.221 An the nozzle plate which is ideally suited to ceramic
electromagnetic printer was built to provide ‘behind processing.
the nozzle’ ink blending for making functional gradi-
ents and preparing combinatorial libraries.222 A bank
Ink and substrate characteristics
of eight electromagnetic valves is used in the aspirat-
ing–dispensing ink-jet printer that forms the basis of Solvent rather than water based inks are generally
the London University Search Instrument for combi- used in industrial marking or coating applications,192
natorial studies in ceramic compositions223 showing since, on non-porous substrates such as plastic, metal
that highly complex multicomponent gradient mater- or glass, the printed image relies on rapid evaporation
ials can be made by ink-jet printing. of the ink solvent.240 Thermal ink-jet printers usually
A micromachined transducer has been designed use water based inks, although non-aqueous inks are
and constructed to operate as a DoD or continuous available.241 Ideally, the liquid ink must be converted
printer and this unit has been used to eject fuels, to a solid structure as quickly as possible by absorp-
dielectrics and biological samples.224 A prototyping tion, oxidation, evaporation, chemical reaction
machine (Model Maker 6PRO, Sanders Prototype or radiation (e.g. UV, infrared, microwave).242
Inc.) based on a two nozzle piezoelectric ink-jet Ultraviolet curable inks produce durable and sharp
printer and intended for making prototypes in wax images on non-absorbent substrates and set rapidly243
has been used for ceramic solid freeforming. Wax but printhead capability, photo-initiator, low toxicity
compositions based on injection moulding suspen- monomer and market needs have hindered the pro-
sions225 can be used to make wax–ceramic shapes gress of UV curable ink-jet development.192
with up to 40 vol.-% powder.226 The apparatus The main properties de ning ink behaviour are
consists of heated DoD nozzles and supply tubes viscosity, surface tension and electrical conductivity.
operating at 120°C over a three axis table.227–230 They The last should be high in the case of continuous jet
dispense a build wax and a support wax that can be printing and low in DoD printers if the ink makes
preferentially dissolved. The equipment has been used contact with electrodes. The viscosity range may vary
to make ceramic casting cores for investment cast- with machine type and ideally the ow should be
ing.231 The same principle is used to make shapes near-Newtonian. A range of 1–10 mPa s is commonly
from ice either by DoD printing or continuous chosen for continuous jet printers and may be lower
extrusion through a nozzle232 but this idea has yet to for some DoD printers. The lower viscosity limits the
be used for ceramic freeforming. ceramic loading in the ink. Drop-on-demand printers
A purpose-built piezoelectric driven printhead has require a stable viscosity during long periods of use,
been used to deposit small PZT tubes from alcohol but this requirement is less critical for continuous jet
suspension.233 Conducting gold tracks have been printers.244 To overcome the temperature dependence
deposited from a piezoelectric DoD printer by using of viscosity, some DoD printers incorporate thermo-
an organometallic ink.234 The same printer has been statically controlled nozzles and some change the
used to create arrays of PZT pillars for 1–3 ceramic– ring signal in response to an ambient temperature
polymer composites235 (Fig. 25) and to freeform sili- sensor.
con carbide from a powder–precursor blend.236 It is often argued, on the basis of Fromm’s work,245
A wide array piezoelectric printhead of the type that surface tension is critical to both the formation
manufactured by Xaarjet Ltd, Cambridge has been and maintenance of discrete droplets. Thus, the ratio
used to make pillar arrays237 and high quality vertical of Reynolds number Re to Weber number We is
walls of about 3 mm height after sintering238 (Fig. 26). given by
A 14 vol.-% zirconia suspension in a mixture of Re (cra)1/2
octane and alcohol was used as the solvent.239 The = . . . . . . . . . . . (7)
We g
prototype Xaar page-wide array printhead (A4 width)
is equipped with constant ink circulation across where a is the ori ce diameter and r, c and g represent
24 Stepless functional gradient of zirconia–alumina made by direct ceramic ink-jet printing (DCIJP) (from
Ref. 189)

relic, is related to cd /c although an equation relating

them has not beensvdeduced.
sv
If c >c, the ceramic tends to migrate to the
sv
periphery of the relic but if c <c this can be avoided
sv
(Fig. 27). Therefore, relics formed on substrates in the
former case, where spreading is appreciable, have a
ring-like appearance due to contact line pinning and
evaporation of solvent.246 In fact, post-deposition
geometrical changes of a ceramic ink droplet have
been studied extensively247 and when c >c the rate
of shrinkage in a drying relic is almost svtwice as fast.
Continuous jet printers, which use an electric eld
to de ect droplets, require the ink droplet to be fully
charged during the charging pulse so that electrical
conductivity of >0·2 S mÕ 1 is needed.212 Polar sol-
vents such as water can yield high conductivity but,
when printing is made on non-adsorbent material
25 Sintered PZT (lead zirconate titanate) pillars and/or a fast drying rate is required, organic solvents,
for ceramic–polymer functional composites such as ethanol or methyl ethyl ketone, are preferred.
made by DCIJP (from Ref. 235) These solvents normally produce less conductive inks
than water and it is common to make additions to
the density, surface tension and viscosity of the ink. improve electrical conductivity.190
This ratio is considered to represent the combination As the printer nozzles are small, e.g. in the range
of surface tension, viscous and inertial eVects. This is 10–220 mm, it is important that particle agglomerates
not supported experimentally227,228 and viscosity or entrained debris, which may clog the nozzle, are
seems to oVer the best guide to the suitability of ink removed upstream by an eYcient ltration system.
for printers. The ink should not dry in the nozzle when the printer
In water based ink, the surface tension of is not in operation.248 Some of the key design para-
72 mN mÕ 1 decreases on blending with dyes, resins meters for the printer and ink are summarised in
and with additives that have a surfactant action and Table 1.
which provide stability of suspension.244 Solvent Silicone release paper, nitrocellulose membrane or
based inks for continuous jet printers also have lower acetate sheet have been used as substrates for ceramic
surface tension. The spreading of the ink droplets multilayer printing. These choices are based largely
over the printing substrate is enhanced if the ink has on the criterion that the substrate can be easily
a lower surface tension. detached from the printed part or that the substrate
In fact, drop-by-drop resolution is dependent on is easily destroyed in processing in order to carry out
the dispersion cd and total c free surface energy
sv sv post-printing operations.
ratio of the substrate.214 When cd /c # 1, there is
sv sv
substantial spreading and the circumferences of drop-
let relics are jagged. The radius of the droplet r can Ceramic ink
be expressed as214 Most developments in DCIJP use commercially avail-
able continuous or DoD jet printers so ceramic ink
A B
3d2 v 1/3
r= j . . . . . . . . . . . (8) has been formulated to mimic the ow properties of
16f the corresponding commercial ink. The successes
The ratio R/r, where R is the radius of the printed
Table 1 Typical design parameters for continuous
jet printer and drop-on-demand jet printer
Parameter Typical range
Continuous jet printer
Nozzle diameter, mm 10–220
Operating frequency, kHz 17–1000
Charging voltage, V 100–300
Deflection voltage, V 1000–18 000
Ink pressure, kPa 0·5–150
Jet velocity, m sÕ 1 5–50
Ink viscosity, mPa s 1–20
1
Ink surface tension, mN mÕ 25–70
Ink conductivity, S mÕ 1 >0·2
Particle size, mm <1
Drop-on-demand jet printer
Nozzle diameter, mm 20–100
Droplet volume, pL 50–500
Operating frequency, kHz 3–25
26 Sintered zirconia model of maze at Hampton
Court Palace showing vertical walls can be Droplet velocity, m sÕ 1 3–15
Resolution, dots mÕ 1 7000–75 000
made by DCIJP (from Ref. 238)

27 Droplet relics and energy dispersive X-ray traces for zirconia ink a with and b without particle
migration on drying (from Ref. 246)
show that ink-jet printers are surprisingly forgiving agitation (using ultrasonic baths or high power ultra-
in terms of the liquids they will dispense. With more sonic probes) dispersion is produced by pressure
than one nozzle, several ceramic inks can be delivered waves that cause cavitation and de-agglomeration of
for fabrication of ceramic composites, graded micro- ocs. This method is eVective and fast for dispersing
structures, microcircuits and micro-engineered cavi- ceramic powders in suspensions and is suited to the
ties.188,189,216 The need for supports for cavities and screening of small samples of ink.210,213,249–251 For
overhang features, which is a problem faced by most example, 180 s of ultrasonic treatment was found to
solid freeforming methods, can be overcome with the be equivalent to 1 h of conventional ball milling252
use of fugitive carbon ink deposited simultaneously and large ocs were broken down into particles close
with the ceramic ink.216 to the initial size distribution.253 At a given frequency,
Most ceramic inks are non-aqueous, but there are de occulation is a function of the ultrasonic power
a few examples of aqueous based inks.218,219 Their and treatment time as well as temperature252 but,
slow drying rate is a limitation. In most cases, as well beyond a certain power threshold, ultrasonic disrup-
as a commercial dispersant, at least one other poly- tion may cause coagulation instead of dispersion.253
meric component is used to sustain the integrity of The use of a high shear mixer, e.g. twin roll mill,
the built object. Un lled pre-ceramic polymer solu- followed by ultrasonic treatment was found to
tions can also be ink-jet printed as precursors to enhance homogeneity and stability of dispersion.210
SiC.236 A high energy bead mill using ne (e.g. 300–500 mm)
A suspension containing solvent, dispersant and media has provided high quality inks for pillar
powder is initially prepared. Agglomerates are broken arrays235 and for use in the Xaar multinozzle
down by the use of a twin roll mill, ultrasound or printer.237–239
high energy bead milling or a combination of The order of addition of the ink components during
these.235,249,250 A dispersant is used to stabilise the mixing may have a signi cant eVect on their viscosity
suspension by adsorption on the powder surface. as well as the strength and density of the un red and
Other additives (e.g. the binder and plasticiser) are sintered parts203 for two reasons. First, reactions
often added in a second stage of mixing. In ultrasonic between the dispersant and other components may
aVect the adsorption capability of the dispersant on colloidal suspension, the shape changes during drying
the powder surface. Second, since adsorption is a are complicated by the accumulation of particles near
competitive and slow process, the organic components the solid/liquid/vapour boundary.247,258,259 As shrink-
that are added rst must be replaced by dispersant age normally accompanies drying, the diVerent drying
for eVective stabilisation. kinetics mentioned above aVect the shape and spacing
Ink management requires attention to cleanliness, of a series of droplets deposited near to one another
ltration and de-airing. After dispersion, the ink can in DCIJP.247 The factors aVecting the behaviour
be left undisturbed to allow sedimentation of larger of a droplet deposited on a horizontal, non-porous
agglomerates before decanting,210,216 the supernatant substrate include the wetting characteristics of the
being used for printing. Before printing, the ink can substrate,247,257,260 atmospheric conditions,261,262
be ltered to remove ocs or debris not eliminated temperature,263 the presence of surfactant231 and the
during sedimentation as they may block the printer size of dispersed particles in the droplet.264
nozzle. The printed parts, after drying, are pyrolysed to
The main limitation of DCIJP is the high liquid burn out organic components before sintering. The
content in the ink, which inevitably slows down the two main variables for binder removal are debinding
forming rate because of the long drying time required atmosphere and heating rate. The low thickness of
before the next layer is printed. Although inks con- printed parts means that the binder and the plasticiser
taining up to 35 vol.-% ceramic have been printed,228 can often be removed rapidly. Parts with aspect ratio
successful printing with commercial DoD printers has as high as 90 have been printed and sintered with
used inks containing up to 15 vol.-% solids. Drying minimal distortion.210 Pyrolysis and sintering did not
can be enhanced by a variety of methods including change the shape of the components produced by
varying the time between printing layers, forced con- printing.216
vection of both cool (24°C) and hot (90°C) air or by
using a heated substrate (60°C), but accelerated
drying can detrimentally aVect the quality of printed Removal of organic vehicle
parts.254
Clearly, the present state of DCIJP restricts it to Most of the solid freeforming pathways for ceramics
relatively thin components. A problem associated involve conveying ceramic particles in an organic
with long periods of printing is that the properties of medium such as an oligomer or polymer. This must
the ink may change and lead to instabilities in the be removed before sintering and fortunately there is
printing process.255 Because of evaporation, the prop- a vast literature on binder removal from injection
erties of the ink certainly change after printing on a moulded and tape cast ceramics that can be applied,
continuous jet printer (Table 2). mutatis mutandis, to solid freeformed ceramics. Thus,
Ripples on the top surface, which are attributed to in direct stereolithography, the organic vehicle that
the droplet drying kinetics, have often been observed results from polymerisation is subsequently removed
in printed parts.210,214,215 Other reported printing by pyrolysis. The same applies to the vehicle in the
defects included splattering,214 unde ned boundaries ceramic tape used for LOM and the polymer that
or ‘faded’ prints.219 When a slow drying rate was enables the extrusion freeforming family of processes.
used, improved smoothness on the top surface was Binder must also be removed from the products of
observed.218 Layer position accuracy in the vertical the ink-jet printing family and in certain cases from
direction in DCIJP is a concern214 as the boundaries the powder in indirect SLS. In indirect stereolithogra-
of the printed parts are not constrained by a mould. phy and extrusion, such as those processes involving
Nevertheless, recent work suggests that vertical walls gelcasting ceramics into a freeformed disposable
can be constructed eVectively.238 mould with organic additives, not only the mould
In their investigations of the evaporation of a liquid but also a binder remains to be removed at a later
droplet on a smooth surface, Shannahan and stage.
Bourges256 distinguished three stages. In the rst The following paths are identi ed in binder removal
stage, the droplet diameter remained constant while from ceramic bodies:
the contact angle and height decreased. In the second 1. Evaporation of low molecular weight oligomers
stage, the width and height decreased concurrently without chain scission. This is a zero order process
while maintaining a constant (receding) contact angle. dependent on surface area and involving either
In the last stage, all three parameters decreased as diVusion through an organic phase or uid ow in
the droplet volume diminished to zero as a result of the pore structure.
evaporation. In another study, the contact angle was 2. Thermal degradation of the polymer (as distinct
found to decrease while the width of the liquid/solid from oxidative degradation) in which fragments
interface remained constant.257 If the droplet is a diVuse or, at a later stage, permeate to the free surface
and evaporate. Thermal degradation can occur either
Table 2 Ink properties before and after printing by random chain scission giving rise to a wide range
for 18 ks (Ref. 211) of molecular fragment sizes, as occurs in the case of
the polyole ns, or by depolymerisation (unzipping)
Ink property Before printing After printing
giving a high proportion of monomer, as occurs in
1
Electrical conductivity, S mÕ 0·338 0·403 the acrylic polymers. In some systems, this can be
Viscosity, mPa s 1·1 1·5 made to occur in the solid state.
Surface tension, mN mÕ 1 25 26 3. Oxidative degradation in which the reaction
Solid loading, vol.-% 2·4 2·6 takes place in the surface region and shrinking core
reaction kinetics can be applied. This approach has

the advantage of leaving less residual carbon.
4. Liquid mass transport by permeation through
the pore structure into a porous body or powder bed
that makes contact with the object. This method has
the advantage that no gaseous products are generated
and so the volume of uid that needs to be removed
is much less. It is eVective where the molecular mass
is low enough to provide low viscosity. A high pro-
portion of binder can be removed this way and the
residue adopts a pendular con guration leaving an
open pore structure for nal pyrolysis.
Binder removal from ceramic generally involves a
combination of reaction and mass transport kinetics
and has been widely quanti ed. Shengjie et al.265 give
a summary of the quantitative work in this area in
their introduction. The whole topic has been reviewed
extensively.266,267 However, it is pertinent to note that 28 Calcium phosphate implant made by indirect
the decomposition characteristics of polymers are SLS (reprinted from Ref. 287, ©1999, with
in uenced by inorganic compounds and, when ne, permission from Elsevier)
high surface area powders are used, even ceramics
thought to be ‘inert’ can have a catalytic eVect on
reaction rates.268 In functional ceramics which tend biomechanical analysis.279 Models of the structure of
to contain transition metals, the catalytic eVects, the ear allow a surgeon to become familiar with the
particularly in the presence of oxygen, are likely to individual anatomy of each patient.280 Solid freeform-
be much greater. ing models also assist in maxillofacial surgery.281,282
The time for binder removal adds signi cantly to The accuracy of a model of a child’s skull made from
the solid freeforming manufacturing time for ceramics Nylon by SLS was less than 1 mm in each direction.283
and this is especially the case where the freeformed In tooth transplantation, a duplicate of the donor
component contains thick sections. In some appli- tooth created from CT data assists pre-contouring of
cations of solid freeforming, such as the latticework the alveolar bone and hence reduces the extra-oral
described above, the cross-sections from which time of the donor tooth to about 8 min.284
organic binder is removed are submillimetre and high MedLAM, a proprietary LOM process, has been
heating rates can be used giving rise to rapid debind- used to prototype bioceramic implants with tailored
ing. Among the defects that can occur in debinding porosity and these can serve as sites for bone forma-
of ceramics is the deformation under gravity as com- tion and tissue regeneration.285 A suspension of cal-
ponents with low powder volume fraction are heated. cium polyphosphate in a photocurable resin and
Resistance to deformation relies on the develop- dispersant was used to make porous implants by
ment of a yield stress269 which is strongly dependent stereolithography followed by thermolysis to remove
on both volume fraction and the eYciency of the resin and then by sintering.286 Calcium phos-
dispersants.225 phate powder coated with a methylmethacrylate–
butylmethacrylate copolymer has been assembled by
indirect SLS into a porous implant. The structure,
Solid freeforming applications in with hexagonal pores, is shown in Fig. 28. After
medicine in ltration with phosphate, sintering at 800°C and
One of the areas where solid freeforming methods implantation it was replete with mature bone growth
have much to oVer is in medicine.270 Its particular after 4 months.287 An indirect stereolithography
value lies in the ability to use data generated from method using epoxy resin moulds has been used to
computed X-ray tomography, sometimes edited make porous hydroxyapatite bone graft material from
for shrinkage, for the creation of individual pros- CT data.69
theses.271,272 Selective laser sintering has been used Superb latticework structures have been produced
to make models of human temporal bone.273 by FDM288,289 for bone substitute scaVolds. These
Stereolithography has been successfully used for poly- are shown in Fig. 29 and are composed of polycaprol-
meric implants in cranioplasty,274 but the authors actone with 7 vol.-% hydroxyapatite. Filament dia-
point to the problem of warpage and the long pro- meters in the range 260–370 mm were extruded. In
cessing time. Ceramic implants for orbital oor pros- this application, the staircase defect in FDM does
theses have been made stereolithographically by not appear. In vitro studies showed that the scaVold
photocuring a resin–hydroxyapatite suspension.275 architecture was completely lled by cellular tissue in
Models generated from CT data can be used for 3–4 weeks.290 Similar structures have been made in
surgical planning and teaching.276,277 Accurate physi- other biodegradable polymers for bone scaVold by
cal replicas of the patient’s individual topography can extrusion freeforming using a constant gas pressure
be made.278 The complex architecture of trabecular extruder.291 Sintered ceramic latticework scaVolds can
bone modi ed by osteoporosis can be reproduced on be prepared and ceramic laments of 60 mm dia. after
a macroscopic scale from high resolution CT or sintering can be made by this process,292 but for
magnetic resonance micro-imaging for visual or laments below about 100 mm the cooling is so rapid
29 Polycaprolactone–7 vol.-% hydroxyapatite lat-

ticework for biomineralisation scaffolds
(reproduced from Ref. 288, with permission of
World Scientific Publishing Co. Pte Ltd, ©2000)
that strong welds are not formed. Figure 30 shows a

hydroxyapatite latticework scaVold made in this way,
but with a solvent based suspension that provides
larger welds.293 Solid freeforming methods can also 30 Hydroxyapatite latticework with filament
diameters of 330 mm (based on method
be used indirectly to good eVect. Thus, 3DP has been
described in Ref. 293)
used to make ceramic moulds in which to cast cobalt–
chromium bone prostheses with a graded porous
surface to promote bone attachment and growth.294 to fabricate high density structural ceramics in a
manufacturing pathway. As a majority of the solid
freeforming techniques for ceramics involve powders
Future developments impregnated with polymer or wax, post-processing
While the applications of solid freeforming technology steps, such as binder burnout and sintering, are
to date have been signi cant, improvements in the needed and are accompanied by shrinkages that are
technology in terms of building speed, surface nish, not easily predicted, notably if the powder is aniso-
dimensional accuracy and material properties are tropic in shape. Dimensional accuracy is not just
needed.153 Assessment of solid freeforming techniques in uenced by the materials and the post-processes
in terms of these four requirements has been made but by other factors such as the machine, software
quantitatively for plastic products.12,14,295 For ceramic algorithms, building accuracy and shrinkage compen-
parts, the comparison is largely qualitative25,32,296 as sation. Accuracy, as Kruth et al.153 have stressed, is
developments are more recent. the greatest challenge of future solid freeforming
The forming time, which comprises pre-processing, processes.
fabrication, and post-processing stages, such as binder A new method that oVers the possibility of solid
removal and sintering, remains high297 and there freeforming ceramics with much greater resolution of
needs to be a signi cant unique justi cation for a both composition and shape is electrostatic atomis-
slower process. DiYculties are encountered in most ation (EA). Electrostatically atomised drops can now
layer based processes to achieve accurate deposition, be printed oVering a new method of solid freeforming
be it in spreading ne powder layers or ensuring ceramics (CEAP),299 and this has now been extended
uniform recoating of a new layer of viscous ceramic to a multiple nozzle process (MCEAP).300 A liquid
suspension in stereolithography. This often deter- owing through a capillary nozzle which is kept at a
mines the viability of the process126 and dimensional high voltage with reference to a ground electrode, can
accuracy of the part. be made to electrostatically atomise, producing a
Surface nish is a crucial feature in solid freeform- spray.301 Electrospraying can be carried out in several
ing.295 The rough texture of the nished part results modes302 but the cone-jet mode produces near-mono-
from the ‘stairstepping’ or ‘staircase’ eVect and is due disperse droplets of a few micrometres in size303 and
to the slicing of a sloped or contoured surface. can be used to process ceramic suspensions.304
Adaptive slicing algorithms modify the layer thickness Deposition of ceramic droplets in this way oVers two
to reduce this.298 Another contributing reason for major advantages. Nozzles used in EA can be several
roughness is the raster scan experienced in SLS and hundred micrometres in size and this is almost ten
3DP which results in a horizontal stairstep eVect on times larger than those used in ink-jet printing. The
the cross-section.13 Improved texture can be obtained use of large nozzles prevents blockages and allows
by reducing the laminate thickness296 or by using easier processing of viscous ceramic suspensions con-
secondary operations such as grinding or polishing,106 taining a high level of solids and/or fast evaporating
but these are detrimental to production time and cost. liquids. Despite the use of much larger nozzles, the
Most solid freeforming processes for ceramics were droplet sizes generated are much ner (typically a few
started for prototyping or for investment casting micrometres), usually by an order of magnitude com-
positives, but there is an increasing eVort to use them pared with ink-jet printing. Computer-aided con-
process. The list below is by no means complete but

may help with reading the literature.
ACU atmospheric control unit
AFD adaptable lament deposition
AOM acoustic optical modulator
a BPM ballistic particle manufacturing
CAD computer aided design
CAM computer aided manufacturing
CEAP ceramic electrostatic atomisation
printing
CC contour crafting
CLI common layer interface
CNC computer numerical control
CPS compact prototyping system
CSG constructive solid geometry
CT computed tomography
DCIJP direct ceramic ink-jet printing
DFE data front end
DMD direct metal deposition
b
DMLS direct metal laser sintering
31 Solid freeforming at two scales: a ink-jet DoD drop-on-demand
printed spots containing silica microspheres DSPC direct shell production casting
and b silica spheres arranged by self- EA electrostatic atomisation
assembled layers (reproduced from Ref. 306 EDM electrodischarge machining
with permission of Nature, www.nature.com, FDM fused deposition modelling
©2000) FEM nite element modelling
FGM functionally graded material
HPGL Hewlett-Packard graphics language
trolled deposition of these ner droplets produced by IGES initial graphics exchange speci cation
EA of a ceramic suspension thus gives a much smaller IH integrated hardened polymer
relic size. However, the use of EA in ceramic forming stereolithography
requires the adaptation of the process to suit viscosit- ISLS indirect selective laser sintering
ies well in excess of 100 mPa s.305 LCVD laser chemical vapour deposition
Initial strength measurements on SiC in LOM trials LEAF layer exchange ASCII format
have been disappointing, with strength about 50% of LENS laser engineered net shaping
that expected from conventionally processed parts.151 LIGA Lithographie–Galvanoformung–
On the other hand, Agarwala et al.106 have used FDC Abformung
to fabricate structural ceramic components with LMF laser metal forming
microstructures and mechanical properties compar- LMT layer manufacture technology
able to those of conventionally processed Si N . LOM laminated object manufacturing
3 4
In the creation of hierarchically structured mater- LOM/COM LOM for ceramic matrix composites
ials, those in which composition and structure are LP-CIM low pressure ceramic injection
planned at length scales from the molecular to the moulding
macroscopic, freeforming methods such as ink-jet MEM melted extrusion modelling
printing can deliver composition and shape control MEMS micro electromechanical systems
at the microscale. This approach is emerging in the MCEAP multinozzle ceramic electrostatic
creation of self-assembled structures based on silica– atomisation printing
surfactant suspensions that form ordered arrange- MJM multijet modelling
ments on drying,306,307 an example of which is shown MJS multiphase jet solidi cation
in Fig. 31. MM model maker
MPM model production machine
MRI magnetic resonance imaging
Acknowledgements MTDS multitask operating system
The authors are very grateful to Mrs Sandra Wells PLD planar layer deposition
for word processing this manuscript. The authors PMAC programmable multi-axis controller
thank Dr Suwan Jayasinghe for help with the prep- RBO rough breakout unit
aration of gures. RP rapid prototyping
RPAM rapid prototyping and manufacturing
Glossary of acronyms used in solid RPI rapid prototyping interface
RPPC rapid prototyping process chain
freeforming RPS rapid prototyping system
The literature on solid freeforming has been made SAHP selective adhesion and hot press
confusing to students by the proliferation of acro- SALD selective area layer deposition
nyms. Part of the reason for this is that an acronym SALDVI selective area layer deposition vapour
serves as a marque that de nes proprietorship of a in ltration
SCS solid creation system 35. n. p. fuster: Assem. Autom., 1997, 17, 525–540.
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Solid freeform fabrication of ceramics

B. Y. Tay, J. R. G. Evans and M. J. Edirisinghe

troversially that some processes may be materials

from the component, (ii) the shaping operation is not

laser heating and multiple layer photocuring rely on

3 Schematic representation of stereolithography

drain the excess resin from the completed part.

Extrusion freeforming of ceramics 7 Schematic diagram of fused deposition

9 Control of filament diameter using adjustable

family of processes is novel and is to be distinguished

a tube array; b bellows; c spiral; d curved transducer; e telescoping; f radial actuators

11 Schematic diagram of selective laser melting

pattern on the substrate. It has been used to create

14 Schematic diagram of laminated object

15 Early examples of alumina components made

Research on the use of a non-planar LOM process

Laser chemical vapour deposition

International Materials Reviews 2003 Vol. 48 No. 6

been made by spraying glassy carbon particles pre-

solvent loss is made before recirculation to the

International Materials Reviews 2003 Vol. 48 No. 6

relic, is related to cd /c although an equation relating

International Materials Reviews 2003 Vol. 48 No. 6

reaction kinetics can be applied. This approach has

29 Polycaprolactone–7 vol.-% hydroxyapatite lat-

that strong welds are not formed. Figure 30 shows a

process. The list below is by no means complete but

International Materials Reviews 2003 Vol. 48 No. 6

International Materials Reviews 2003 Vol. 48 No. 6

International Materials Reviews 2003 Vol. 48 No. 6

International Materials Reviews 2003 Vol. 48 No. 6

International Materials Reviews 2003 Vol. 48 No. 6

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