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Advance Forming Tech
Advance Forming Tech
Z.S. Rak
Revisions
A 2 may 2000; Final version
B
Made by: Approved by: Issued by:
ECN Energy Efficiency
Materials Technology
Abstract
Improvement in powder processing and forming technologies is the way to improve the
reliability of advanced ceramics and lower their cost. Therefore a lot of effort is put into the
development of low cost technologies for high volumes of complex-shaped components that
will have the ability to form complex-shaped thin-walled parts. The near-net-shape forming of
advanced ceramics are on the top of the interest. The following forming processes are actually
in the stage of commercialisation or development: pressure slip casting, freeze casting, powder
injection moulding, tape casting/lamination, rapid prototyping, and colloidal processing of
powders. Especially the techniques based on the colloidal processing such as gelcasting,
electrophoretic casting, hydrolysis assisted solidification, direct coagulation casting and similar
are in a great interest due to an ability of reducing the critical defects size originated from
manufacturing route. Specific manufacturing features, advantages, disadvantages and limitation
of these novel processes are described in details in the paper.
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CONTENTS
1. INTRODUCTION 5
2. NEW FORMING TECHNIQUES 7
2.1 Aqueous injection moulding 7
2.2 Centrifugal slip casting 7
2.3 Direct coagulation casting 8
2.4 Electrophoretic casting 9
2.5 Gelcasting 10
2.6 Hydrolysis assisted solidification 11
2.7 Pressure slip casting 11
2.8 Temperature induced forming 12
2.9 Others 12
3. ADVANTAGES AND DISADVANTAGES OF NEW FORMING PROCESSES 13
4. CONCLUSIONS 15
REFERENCES 17
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1. INTRODUCTION
Ceramics materials are, in general, divided into conventional ceramics and advanced ceramics.
Conventional ceramics are growing at a slow rate and some of their branches even show a
decreasing tendency, i.e. refractory materials. In contradiction to the conventional ceramics the
market for advanced ceramics is large and growing continuously [1, 2]. Advanced ceramics are
generally divided into three categories - structural, electronic and coatings. Structural ceramics
include applications such as industrial wear parts, bioceramics, cutting tools and engine
components, and are the fastest growing segment. Electronic ceramics include dielectrics
(capacitors, insulators and substrates), integrated circuit packages, piezoelectric ceramics,
superconductors and magnets, and form the largest share of the advanced ceramics. The total
market size of advanced ceramics was $6.5 B in 1997, of which 71% belongs to the electronic
ceramics, 18% to structural ceramics and 11% to ceramic coatings. The highest average growth
rate, 8.2% per year between 1998-2003, is predicted for structural ceramics [1]. The advanced
electronic ceramics products are in general characterised by a simple shape, are produced in
long series, and available conventional shaping techniques like slip casting, PIM, tape casting,
extrusion, uniaxial pressing are sufficiently good for shaping process. On the other hand, their
main feature is their functionality not mechanical strength, and even an average mechanical
strength is sufficient for their final application. A quite opposite situation is in the field of
advanced structural ceramics. The main parameters characterising these materials are the
mechanical strength and reliability, the products are of complicated shape and therefore near
net-shaping techniques are required for their production (i.e. components of engines, gas
turbines and similar). Therefore all examples of applications, which are referred in this paper are
for structural ceramic products.
Critical factors in the commercialisation of advanced ceramics are the starting materials and the
way they are shaped. Typical defects in ceramic components are often introduced by the powder
itself, and/or in the forming and densification processes [3]. On the other hand there is a general
requirement that all advanced ceramic materials should be characterised by a high mechanical
strength. Therefore there are two lines of approach for improving the mechanical properties of
ceramic materials at the present time [3, 4]. The first approach, according to Griffith's equation
(1), favours reduction of the size of critical flaws, which may consist of residual pores,
inhomogeneities, surface flaws or sintering induced cracks.
Griffith’s equation:
σ = Y (K1c √ ac) (1)
where:
ac – critical flaw size,
σ – bending strength,
K1c – fracture toughness,
Y – shape factor.
The other approach relies on attempts to increase the material's toughness, thus making it less
susceptible to the effects of critical flaws. The first approach tries to improve monolithic
ceramics via the application of new forming techniques, the second approach attempts to
implement concepts aimed at increasing the toughness of ceramic materials. In the latter case
higher fracture toughness values can be reached by utilising e.g. the martensitic phase
transformation of tetragonal to monolithic ZrO2, layered structure, or reinforcement of the
ceramic matrix by whiskers, fibre’s or platelets [4-6]. Shape forming techniques can be divided
into traditional techniques such as dry pressing, powder injection moulding and extrusion, and
wet colloidal forming techniques such as slip casting, tape casting, etc. The reliability of dry
pressing ceramics is limited by defects due to agglomerates. This can be avoided by colloidal
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forming, where ceramic powders can be deagglomerated completely [7, 8]. However most
colloidal forming techniques are limited in the case of larger, complex parts with
simultaneously thin and thick cross sections due to density gradients in the green body. The wet
processing routes provide on the one hand the possibility of breaking down agglomerates but
create on the other hand other problems like the differential sedimentation due to the particle
size distribution in the starting powders. There are a few different approaches to overcome this
problem such as the use of flocculated slurries or coagulated systems [6, 7]. The drawbacks of
these methods are that flocculated and coagulated systems lead to green bodies with rather open
structures and lower green densities, which need higher sintering temperatures to reach the
theoretical density. Therefore, new techniques such as (hot) isostatic pressing, aqueous injection
moulding [9-14], centrifugal slip casting [6, 14-18], direct coagulation casting [19, 21],
electrophoretic forming [22-25], gelcasting [21, 26-31], hydrolysis assisted solidification [32,
33], pressure filtration [34-36], and temperature induced forming [37, 38] were developed in
recent years. The pressure slip casting, electrophoretic forming and centrifugal slip casting were
also included in this overview in spite of the fact that they are well-known techniques in the
traditional ceramics sector. However they are still newcomers in the advanced ceramics world.
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2. NEW FORMING TECHNIQUES
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pore-size distribution. Considering ultrafiltration membranes, up till now the filtration layer is
formed on a support layer, which has larger pore size (1 to 6 μm) and is manufactured by slip
casting or extrusion. Between the support layer and filtration layer, a discontinuous transition of
material properties exists which, however, can be avoided by a gradient structure. To solve this
problem, multimodal suspensions can be used to form a powder compact with a pore gradient if
a particle size segregation can be achieved during the consolidation process. Oxide ceramics are
in general used as materials for ultrafiltration membranes. In this process, a powder dispersed in
a liquid with a stabilising agent, followed by axial rotation in a cylindrical mould for some time.
The resulting cast is dried, released from the mould and sintered. If particles with a narrow
distribution and low degree of agglomeration are used, a nearly random-close packed green
compact can be formed. During centrifugical casting, the large particles form the large pores on
the bottom of the sediment and the small particles form the small pores on the top layer of the
sediment if the centrifugical acceleration is high enough. Ideally the pore-structure in each layer
can be consolidated at the random packing structure of nearly monosized spheres. This pore-
gradient structure is analogous to an asymmetric membrane, which is preferred in the filtration
applications. The resistance of an asymmetric membrane to filtration mass transfer is
determined by the thin top layer. The last layer for ultrafiltration layer can be manufactured also
by the sol-gel technique. This technology lowers significantly a number of production steps in
the membrane technology, results in improved strength of the support material and also lowers a
number of incidental defects. The technology is still in the laboratory stage because instead of
the perfection of the produced tubes higher prizes are serious limitation in mass-scale
production. The second drawback of this technique is the limitation to only circular shapes [17].
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Several other enzymatic reactions such as pectin, casein or protein hydrolysing enzymes are also
useful for coagulating special ceramic suspensions. In case of particle suspensions with high
solid loading the cast components do not undergo shrinkage during coagulation. This allows for
production of complex shape bulk components, even with undercuts to near net shape in
relatively short times (10 to 90 min.) It offers the possibility of low cost production of these
complex shaped parts with extremely high strength and high reliability. The comparison of
gelcasting and DCC forming techniques made by CERAM TEC AG, Germany proved the
superiority of the DCC method [21]. Alumina ceramics produced by the DCC technique,
sintered at 1400oC, were characterised by a density of 3.985 g/cm3, a mean bending strength of
623 MPa and a maximum flow size as low as a few micrometers.
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The EPD is considered to be a powerful forming technique for three reasons;
• it is extremely versatile,
• it is a low cost process,
• it is reliable.
Problems that could be faced during the EPD process are: unwanted water electrolysis, galvanic
reactions and water electro-osmosis. However the simplicity of the process and the capability of
depositing metals, ceramics and polymer by electrophoresis opens great possibilities for
application in different fields such as electroceramics (SOFC, multilayered capacitors, sensors,
actuators, etc), structural ceramics (layered composites, long fibre CMC, functionally graded
materials, laminated ceramic composite tubes, etc.) and protective coatings onto metals (EPD
of sol-gel solutions or suspensions) [23-25]. This technique is already used commercially in
traditional ceramics (electrophoretic spray coating of sanitary wares, enamel electrophoretic
deposition, etc.).
2.5 Gelcasting
Gelcasting (GC) is a new shaping process for advanced ceramic materials. Proof of concept was
demonstrated by the scientists from Oak Ridge National Laboratory, USA in 1985 using non-
aqueous systems. Development of an aqueous process using acrylamide as monomer was
completed in 1988 [26]. However, concerns regarding health, safety and disposal of acrylamide
caused industrial rejection of the process (acrylamide is a neurotoxin). Development of a low
toxicity process was initiated to deal with the lack of acceptance, and it was fully demonstrated
in 1990 [27]. In the gelcasting process, a small amount of organic monomer and cross linker is
added to the ceramic aqueous slurry. The most useful systems are based on the monofunctional
monomers methacrylamide (MAM), methoxy poly(ethylene glycol) monomethacrylate
(MPEGMA), and n-vinyl pyrrolidone (NVP), the difunctional monomers methylene
bisacrylamid (MBAM) and poly(ethylene glycol) dimethacrylate (PEG(1000) DMA), and the
initiators ammonium persulfate/tetramerthyl ethylene diamine (APS-TEMED), azobis ([2-(2-
imidazolin-2-yl)propane HCl (AZIP), and azobis (2-amidinopropane) HCl (AZAP). None of the
monomers interact adversely with standard ceramic processing aids such as dispersants and
defoamers. Solids loading as high as 55-60 vol.% were achieved in alumina slurries and 45-57
vol.% in silicon nitride suspensions using these systems [2]. Upon heating, the monomer
polymerises, and the resulting gel (which is ca. 90% water) stiffens the ceramic powder slurry
into the shape mould. Gellation times are as short as 15 min for turbine wheels. The gelled
powder is then easily dried to remove the water, leaving a powder compact with an open pore
network and 2-4 wt% dried gel. The gel is easily removed by a short pyrolysis cycle. The
gelcasting process is 50-80% faster than the slip casting technique, generating a more uniform
powder packing, having a much higher part strength after forming and after drying, and
requiring simpler moulds (no need for dewatering surfaces). The gelcasting is more amenable
for to automation than the pressure slip casting process of complex shapes. However
densification is still an issue. Gelcasted parts typically shrink 23% during densification,
resulting sometimes in distortion in the densified parts. Gelcasting starts to be used not only for
manufacturing of complicated shaped dense products such as parts of turbines but also for
manufacturing of porous ceramic objects [2, 27-31]. The new shaping technique is not limited
to the USA but recently very broadly tested in other countries like Germany, Brazil, China,
Spain, Poland, and others [21, 28-31]. The most advanced works in the field are already in the
phase of commercialisation. AlliedSignal Ceramics Components (Torrance, CA, USA) working
together with ORNL (Oak Ridge, TN, USA) has developed an automated gelcasting fabrication
process of production ceramic turbine motors [2].
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2.6 Hydrolysis assisted solidification
The Hydrolysis Assisted Solidification (HAS) process was developed by the scientists of the
Josef Stefan Institute in Ljubljana, Sl [32, 33]. The process is a sort of cross between hardening
of cementitious products, DCC and gelling, providing some benefits of each. The process is
based on thermally activated and accelerated hydrolysis of aluminium nitride (AlN) added to
highly concentrated ceramic suspensions:
AlN + H2O → Al(OH)3 + NH3 (4)
During the hydrolysis of AlN, water is consumed. The solid loading will increase as water is
bound into the metal hydroxide and ammonia is formed, which in turn may increase the pH of
the suspension (the pH is shifted toward the isoelectric point of the alumina). Both mechanisms,
i.e. water consumption and shift in pH, can be exploited for solidification of an aqueous
suspension in a die. Furthermore, aluminium hydroxide, which is another reaction product
obtained on AlN hydrolysis, gels on heating as well, which additionally assists in the
solidification process and increases the strength of the moulded green body. The benefits of this
process are excellent rheological properties, fast solidification, and high degree of density. The
drawbacks include limited time and temperature stability, sensitive feedstock preparation, heat
transfer during solidification and need of additional equipment to collect and neutralise
ammonia. Additionally, the process is not suitable for all types of ceramics (introduces
alumina). The technology is in an industrial scale-up phase.
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one may be that existing conventional technologies are well established in this industry and that
another shaping technology would be difficult to justify because of the capital investment
required.
2.9 Others
The above overview of new forming techniques for advanced structural ceramics is not
complete. There are some other forming techniques which have been neglected in this overview
due to a lower potential for implementation in industrial practice such as freeze casting [39],
adiabatic casting [40], AIM using methyl cellulose binders gelling during heating [41], etc.
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3. ADVANTAGES AND DISADVANTAGES OF NEW FORMING
PROCESSES
Most of the advantages, disadvantages and process limitations which could be labelled as
specific characteristics of colloidal processing technologies arise from the solidification
principle exploited while all the others are inherited from the parent technologies, i.e pressure
slip casting from pressure casting, etc. In Table 1 a provisional list of major benefits, drawbacks
and specific limitations of the discussed variants of the wet processing route are presented.
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Environmental aspects of all the presented colloidal processes using water as a liquid vehicle to
replace organic solvents and binders was not discussed in the paper but these are obvious.
According to the author a final successful application of a specific technology to production
practice will be decided, however, by an ability for automation because if the market for
advanced ceramics will be developed continuously, then it will be necessary to go to
automation.
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4. CONCLUSIONS
The following conclusions can be drawn:
• The ceramic components manufactured by the reviewed wet forming techniques are
characterised by a lower number of smaller processing defects than in the case of ceramic
components manufactured by pressing, extrusion or PIM. In the former case the maximum
defect size does not exceed 10-20 μm, in the latter case this is approximately 40-50 μm, or
even higher [21].
• The biggest potential is possessed by those forming techniques which are suitable for
automation, i.e. gelcasting, aqueous injection moulding, or suitable for the production of
ceramic components with extremely good mechanical properties and high reliability, e.g.
direct coagulation casting.
• The use of water as a liquid vehicle is the most powerful attribute of colloidal processes
from the environmental point of view.
• The colloidal processing of powders and automation are the key factors of the future for
advanced ceramics.
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