Lecture Notes Chapter 7

Book Carter & Norton:

• Chapter 23: 23.1 - 23.11
• Chapter 25: 25.7
• Chapter 27: 27.1 - 27.4

Louis Winnubst

e-mail: a.j.a.winnubst@utwente.nl
 The Ceramic Fabrication Process

Powder Preparation

Compaction Processing
Microstructure
Sintering
Green
compact
Post Treatment
 Forming of the “green” compact

Powder • Sufficient strength for further handling

• Several processing techniques

Compaction
Processing
3 main routes:
1. “dry” powder: Pressing
Sintering 2. Casting: Tape/slip casting - ”Suspension”
3. Plastic forming: Extrusion/injection moulding
”Paste”

Post
Treatment
 Aspects related to compaction processing

•Powder Characteristics (particle size, particle morphology)

•Interactions between powders:
• Dry powders: powder mechanics/agglomerate strength
• In suspension: colloid chemistry (suspension stability)
• Rheology of suspensions and pastes

•Drying and binder burn-out (thermal processing)

•Properties of the green compact like:

•strength, deformability
 Compaction processing

Dry Pressing

Slip Casting
Freeze Casting Increasing amount
Casting of additives
Tape Casting
(stabilizers-binders)
Gel Casting

Extrusion
Plastic forming
Injection moulding
 Compaction Processing

Additives: Binders, Stabilizers and Plasticizers

• Binders: Provides the green compact with sufficient strength
to survive further handling (Compaction)
• Stabilizers: Uniform particle distribution during green forming
(Important for Casting like Slip and Tape Casting)
• Plasticizers: Provides plasticity to the powder mass during
the shaping process (Extrusion, Injection moulding)
 Pressing

• Dry (uni/bi axial) pressing (23.4)

• Hot pressing (23.5)
• Cold isostatic pressing (23.6)
 “Dry-bag”
 “Wet- bag
• Hot isostatic pressing (23.7)
Sections from book: “Ceramic Materials - Science and Engineering”
ed. by: C. Bary Carter and M. Grant Norton

Link to this book is on Canvas

 Dry Pressing

•Uniaxial/Biaxial

Powder reorganisation in the

mould by external pressure
Change in morphology
(agglomerates/granules)

Simple-cheap method

See also book Carter and Norton Figure 23.1

Uniaxial Pressing – inhomogeneities in compact

Inhomogeneous density
distribution in green compact
 Uni-axial / Bi-axial pressing
A Density gradients can occur when:
Dry Pressing

•Isostatic

Powder reorganisation in the mould

by external pressure from all sides

Cold Isostatic Pressing (CIP)

• “Dry-bag”
• “Wet- bag”
 Isostatic Pressing

Dry Bag Wet Bag

 Dry bag isostatic pressing

Mold is an integral part of the press

Fabrication of spark plugs

 Wet bag isostatic pressing

A powder in a bag (rubber

mould) is placed in a pressure
vessel (water or oil)

↑ Limited pressure gradients

↑ Uniform density
↑ Low tooling costs
↑ Interesting for laboratories

↓ Green machining necessary

↓ Long cycle times
↓ Limited geometric shapes
Compaction behaviour of agglomerated powders

•Primary particle
or crystallite

•Aggregate (strong agglomerate)

Strong (chemical) bonding between
particles

•Agglomerate
Weak bonding
 Nano-structured zirconia prepared by precipitation
Influence of gel-washing on agglomerate structure/compaction behaviour

Metal salt solution

(ZrCl4 + YCl3)

Nucleation
burst
Hydrolysis in excess
ammonia (pH > 12)
Amorphous metal-
hydroxide gel SEM: agglomerates
Water/Ethanol washing
(control agglomeration)

Drying

Calcining
Weakly agglomerated powder
If washing with ethanol is performed TEM: crystallites and aggregates
 Compaction behaviour of agglomerated powders

Pressure compaction curve

•Isostatic pressing
•Measure density at several pressures
•Graph: log (P) versus relative density

Scheme of particle packing in a

compact prepared from
agglomerated powders
Initial stage of compaction
 Compaction behaviour of agglomerated powders

ZrCl4 + YCl3 Gel washed with water and alcohol

Hydrolysis

water/ethanol
washing

Drying

Calcining

▼: Pore size distribution determined

Change in pore-size distribution during isostatic compaction
Gel washed with water and alcohol

Pore size distribution determined by: - N2 adsorption/desorption

- Hg intrusion porosimetry
Low Pressures (<Py = yielding point)
• Rearrangement of agglomerates
• Internal aggl. structure remains intact
• Pores < 20nm do not change in size and volume

Py: Disruption of agglomerates

It is a measure for agglomerate strength

P > Py: rearrangement of internal agglomerate structure

Cumulative pore size distribution
Strong Agglomerates

Weak Agglomerates
 Strong Agglomerates (Only water washing)

Green Compact
Sintered Compact

•No fracture of agglomerates during compaction

•Agglomerate boundaries remain visible after sintering
•Low density and many (micro)cracks after sintering

Powder
 Hot Isostatic Pressing (HIP)

• Pre-forming (e.g. by cold pressing) • Pre-forming (e.g. by cold pressing)

• Encapsulating (“canning”) in a • Sintering (pressureless)
deformable container  Sample has only “closed pores”
• HIP • HIP: post HIPing
 Compaction processing

Dry Pressing

Slip Casting
Freeze Casting
Casting
Tape Casting
Gel Casting

Extrusion
Plastic forming
Injection moulding
 Suspension Processing

Slip Casting

•Powder + solvent + deflocculants

•Suspension/Slip stable suspension!
•Slip is poured in a porous mould
•Solvent is extracted by the mould
(capillary forces)

Release of a cast
from the mould
Slip Casting
 Deflocculants

•Deflocculants (stabilizers) are additives, which causes the process of

defloculation (or the break up of floccules/agglomerates)
 Deflocculation is the opposite of coagulation

•Flocculation or the presence of flocculants

•Flocculants can be regarded as (weak) agglomerates
 Suspension Processing

Deflocculation - Stable Suspension

Electrostatic stabilisation
DLVO: Electrostatic repulsion + Van der Waals attraction
 Surface and Zeta (ζ-) potential
 Debye length (1/κ)

Surface potential
as function of pH
Other ways of stabilisation
Repulsion of particles
 Slipcasting – Driving force for cast formation
 Capillary suction by the substrate drives particles to the
interface suspension-substrate.
 Capillary force a/o depends on pore radius of substrate
 Slipcasting – Cast formation

Important parameters :
 Slipcasting – Cast formation; Solvent removal

•Porous mould: Plaster of Paris (2CaSO4.2H2O)

•Water goes to the porous mould via capillary forces
dP dP
•Flux: J = −K : water pressure gradient
dx dx

•Pressure gradient is determined by pressure at slip

surface (= 1 atm) and capillary force (= 2γ/rc) of mould
•Slip growth rate (dx/dt) is proportional to flux:
∆P 2γ dx
J=
−K =
−K =
C
x rc x dt
•Integrate: x2 is proportional to t
 Thickness of the cast (x) is proportional to t1/2

Section 25.7 (book Carter and Norton)

http://www.britannica.com/EBchecked/media/260/Stages-in-the-slip-casting-of-a-thin-walled-whiteware
 Typical advanced ceramics made by slipcasting
Typische slibgietproducten
 Compaction processing

Dry Pressing

Slip Casting
Freeze Casting
Casting
Tape Casting
Gel Casting

Extrusion
Plastic forming
Injection moulding
 Tape casting

Introduction

 Suitable for manufacturing thin sheets: 1 µm – 1 mm

 Multi-layer systems possible
 Product examples:
− Ceramic capacitors
− Piezo-electric ceramics
− Solid electrolytes for energy conversion
Tape casting - important (process) parameters
 Characteristics of the starting powder
− Particle size and size distribution
− Particle form
− Specific surface area
 Characteristics of the casting suspension
 Characteristics of the slip
 Tape casting (doctor blade) process
 Drying process
(Relative thick) Green product after tape casting
 Preparation and Characteristics of the Casting - Suspension

Suspension
 Solvent: aqueous or organic
− Most cases non-aqueous solvent
Solvent Ceramic Dispersant
powder

Milling
 Dispersants (deflocculants)
Binder Mixing Plasticiser
− Avoid settling of powder particles
− Stabilisation mainly by steric hindrance Degassing

Tape
Casting

Drying

Shaping

Sintering and
Binder burn-out
 Other ways of stabilization/deflocculation

Electrostatic stabilization not effective

when organic solvents are used
 Preparation and Characteristics of the Casting - Slip
 Binders
− Holds ceramic particles
together until sintering Solvent Ceramic Dispersant
powder
 Plasticizers
− Increases flexibility of green tape Milling

 Other processing agents: Binder Mixing Plasticiser

− Wetting agents Degassing
− Defoamers
Slip (or Slurry)
− Release agents Tape
Casting
 Slip Parameters
Drying
 Solid concentration
 Temperature Shaping
 Rheology
Sintering and
 Viscosity: 5 – 25 Pa.s
Binder burn-out
 Typical tape-cast slip composition

Ceramic powder Alumina, Zirconia, BaTiO3, etc. 43 %

Solvent Ethanol 46 %
Dispersant Solsperse 20000 (a poly alkoxide) 1%
Dispersant Menhaden fish oil 0.5 %
Binder Poly(vinyl butyrate) (PVB) 6.5 %
Plasticizer Butyl benzyl phthalate (BBP) 3%

See also Table 27.1 Carter and Norton

Maciej Domanski
University of Twente
The Tape-Casting Process

Solvent Ceramic Dispersant

powder

Milling

Binder Mixing Plasticiser

Degassing

Tape
Casting

Drying

Shaping

Sintering and
Binder burn-out
Doctor Blade Process during Tape Casting
 Doctor Blade Process
A tape-cast equipment
casting suspension

Thickness (δ) of the tape depends on: •Blade height (h) and width (W)
•Belt velocity (v0)
•Suspension viscosity (η)
•Pressure difference
Newtonian fluid: (∆P; determined by L)
 Drying Process

 Evaporation rate should be slow

 Temp. of drying atmosphere at inlet < BP of solvent
 Drying in counter flow
 Drying techniques
− Electric heaters
− Microwave
− IR
 Tape casting - Summary
 Keywords
− Homogeneity
− Particle size and size distribution
− Stable suspension in non-aqueous medium
− Additives
− Rheology
− Controlled evaporation of the solvent
http://www.britannica.com/EBchecked/media/262/Steps-in-doctor-blading-a-tape-casting-process-
employed-in
 Multilayer Ceramic Capacitor
MLCC

6 parallel capacitors

High capacity in a small volume

 Multilayer Ceramic Capacitor

http://www.murata.com/products/emicon_fun/2011/06/cap_en28.html
 Making micrometer-sized structures

Micro wells or micro pillars on silicon wafer used as a mould

Maciej Domanski, Louis Winnubst, Regina Luttge, Edwin Lamers, X. Frank Walboomers, John Jansen and Han
Gardeniers, J. Mater. Sci., Materials in Medicine, 23 [7] (2012) 1637-1444.

“Production and characterization of miro- and nano-features in biomedical alumina and zirconia
ceramics using a tape casting route”
Ceramic micromoulding utilizing tape casting

Silicon mould slurry

Anti sticking layer

on silicon (various
materials were
tested : carbon Slurry composition:
~70 % of ceramic powder i.e
fluorides, metals, Alumina
metal oxides) ~30 vol% of organic binder i.e.
+ additives: deflocculants, plasticizers
dispersants

A ceramic slurry containing

binder, powders etc. is Drying and
Debinding and
mixed for 24 hrs and casted demoulding of
subsequent sintering
on top of the mould the green tape
Ceramic micromoulding utilizing tape casting

Silicon mould slurry

Anti sticking layer

on silicon (various Green tape
materials were Sintered ceramics with micropattern
tested : carbon Slurry composition:
~70 % of ceramic powder i.e
fluorides, metals, Alumina
metal oxides) ~30 vol% of organic binder i.e.
+ additives: antiflocculants, plasticizers
dispersants

A ceramic slurry containing

binder, powders etc. is Drying and
Debinding and
mixed for 24 hrs and casted demoulding of
subsequent sintering
on top of the mould the green tape
 Micromoulded Alumina (Al2O3) - Holes

Mould

SEM photos of micromoulded

Alumina surfaces.
Starting from AKP-30
Alumina micromoulding - Pillars

Pillar diameter ~ 6,4 μm

Pillar height ~ 1,4 um

Maciej Domanski
 Compaction Processing

Dry Pressing

Slip Casting
Freeze Casting
Casting
Tape Casting
Gel Casting

Extrusion
Plastic forming
Injection moulding
 Extrusion

• Ceramic powder + binder

• High viscous paste
• Pressing through an extrusion die/nozzle

Auger extruder
Piston or ram extruder
Fig 23.10 “Ceramic Materials -Science
and Engineering” (Carter & Norton)
 Paste Processing

Extrusion products

• Cylindrical symmetry:
tubes, rods, capillaries
• Products with controlled cross-section
(high tolerance)

Translucent
Alumina tubes

Alumina Ceramics in
discharge Lamps
 Alumina ceramics in discharge lamp

• extrusion

 cylinder-built geometries
so-called 5-piece concept
 monolithic body: compressive joining (sintering)
 Extrusion products
Extrusie

Extrusion of a multichannel ceramic membrane carrier

 Extrusion products – Membrane module

Tubes/Single channel
 Ceramic Hollow Fibres – Spinning/Extrusion
 A method derived from polymeric membranes
− Wet spinning of a viscous polymeric solution
 A versatile way for fabrication of dense and porous
ceramic fibres
 Fibre diameter: Typical 2 mm or less

 Phase-Inversion tape casting

 Hollow fibre processing – Polymeric fibres
 Phase inversion: Add polymer solution to non solvent - Wet spinning
 Ternary phase diagram:
P(olymer)
S(olvent)
N(on)S(solvent)

 Ceramic analogue? Phase separation liquid-liquid demixing

- Add particles to polymer and solidification
solution
Viscous polymer solution

Region of stable homogeneous

polymer solution

 Polymer-rich phase
 Polymer-lean phase - (macro) pore former
M. Bikel, University of Twente
 Inorganic hollow fibres - Fibre spinning
A fast way for making “tubes” with high Area/Volume (A/V) ratio
• Combination of extrusion and phase inversion
 Polymer solution containing an inorganic powder
 Spinning mixture is forced through a spinneret (extrusion die)
 Add mixture to non solvent: Induce phase inversion
bore liquid
 Washing, drying, (non-solvent)
 Thermal treatment: debinding, sintering
polymer solution
Inorganic powder Stainless Steel (316L), Ni,
SiC, Al2O3, YSZ
Polymer Polyether-sulfone (PES) spinneret

Solvent N-methyl-2-pyrrolidone (NMP)

Viscosity modulator Polyvinyl-pyrrolidone (PVP) Coagulation
bath
Non solvent Water coagulation bath 9
(non-solvent)
Typical hollow fiber fabrication setup

spinneret

© Patrick de Wit,
University of Twente
 Ceramic Hollow Fibres
Wet spinning: co-extrusion/phase inversion
Nitrogen

 Process steps and process parameters:

particle size bore

agglomeration
type of polymer H2O
spinneret
mixing Air gap

rheology polymer/powder ratio Coagulation bath

pressure
air gap

coagulation bath time temperature

bore liquid
sintering program
 Phase inversion hollow fibre: Typical microstructure
Green Sintered
 Macrovoids in green compact remain
after sintering
 Diameter decrease: 73%

 Versatile method for different materials

 Challenges
- Removal of macro voids
- Reduction of radial dimensions
- Improve mechanical strength of the fibers
 Tape casting involving phase inversion
 Polymer solution containg inorganic powder
 Casting (doctor blade) on mylar sheet
 Immerse in water (= non solvent)  Flexible, easy-to-handle green tape
 Washing, drying
 Binder burn-out: 800 ºC
 Sintering: 1500 ºC

Inorganic powder Al2O3

Polymer Polyether-sulfone (PES)
Solvent N-methyl-2-pyrrolidone (NMP)
Viscosity modulator Polyvinyl-pyrrolidone (PVP)

Hong Fang , Chunlei Ren , Yaoge Liu , Detang Lu , Louis Winnubst , Chusheng Chen
Phase-inversion tape casting and synchrotron-radiation computed tomography analysis of porous alumina,
Journal of the European Ceramic Society 33, [10] (2013) 2049 – 2051
 Phase-inversion tape casting
 Analysis of morphology by synchrotron-radiation computed tomography
(SR-CT)
• Spatial resolution: 3.7 μm SEM

Cross section:

Top layer:

 Elongated finger-like large pores

Hong Fang , Chunlei Ren , Yaoge Liu , Detang Lu , Louis Winnubst , Chusheng Chen
Phase-inversion tape casting and synchrotron-radiation computed tomography analysis of porous alumina,
Journal of the European Ceramic Society 33, [10] (2013) 2049 – 2051
 Paste Processing
Injection Moulding

• Powder + thermoplastics
• up to ca. 50% organic additives
• Plastic behaviour of paste
• Moulding process: SiC rotors
- Control of rheology by left: as moulded
temperature/applied force right: after sintering

•Complex shapes
•Large quantities
 CIM (Ceramic Injection Moulding) Process

MIXING
POWDER BINDER

GRANULATION

DEBINDING & SINTERING

INJECTION
MOULDING

COMPONENT
Injection moulding equipment
 When injection moulding?
 Complex geometries
 Narrow tolerances necessary
 No or few post treatments
 Sinter shrinkage
Linear shrinkage ~ 20 %
Volume shrinkage ~ 50%
 CIM-process

Product:
• Size tolerances ± 0.3- ± 0.1 %
• Surface roughness: 0.4-1.6 µm
• Density 97.5 - 99.5 %

COMPONENT
Injection moulding: Typical examples
Injection moulding- lamp envelopes
 Summary

https://slideplayer.com/slide/3806524/
 Forming of the “green” compact

Dry Pressing

Slip Casting
Freeze Casting
Casting
Tape Casting
Gel Casting

Extrusion
Plastic forming
Injection moulding