Lecture: Mineral Materials I: Ceramics

Prof. Jesus Gonzalez-Julian

RWTH Aachen University
Institute of Mineral Engineering
gonzalez@ghi.rwth-aachen.de
Content

• Powder processing - Methods - Wet processing, moist processing, dry processing

− Drum mill
− scouring mill
− Agitator ball mill (Attritor)
− Clay grater
− vertical roller mill
− Countercurrent jet mill
• Particle shape and particle size distribution
• Stress during comminution
• Suspension preparation - organic additives, dispersing mechanisms
• Granule production - spray dryer
• Shaping - Partitioning
− Uniaxial pressing
− Isostatic pressing
− Slip casting
− Tape casting
− Extrusion
− Injection moulding
Advantages and disadvantages the ceramics

Then, ceramics are versatile and wonderful…yes, but difficult to process

Forging Melting and shaping Ductility / rolling Easy machining

a Ceramic dream a Ceramic dream a Ceramic dream a Ceramic dream

Ceramics cannot be forged, melted and shaped, they are not ductile and difficult to machine
Production steps - Powder preparation
How do you suggest to produce some powders from these materials?

Metal Ceramic Polymer

Do you think fine (small) or coarse (big) powders

have an influence in the processing of a component?

And in the energy consumption?

Production steps - Powder preparation

Green Hard
Powder Processing Engineering Shaping sintering
processing processing
Powder preparation

Ceramic materials have high hardness - this makes the preparation of the starting powder complex.

▪ Hardness makes difficult the milling process and will cause severe wear and damage

▪ Brittleness, on the other hard, will facilitate the milling process

▪ But of course, every material is different

▪ Several points to consider depending on the final quality and application

▪ Important! During the milling process to alter (or even destroy) the composition or features of
your material

▪ Milling process: (typically) high energy, high temperature, abrasion and impacts
Powder preparation - background and goals

➢ Crushing (obtaining powders) ➢ Material consistency:

▪ Hardness
➢ Homogeneous mixing ▪ Plasticity

➢ Addition of organic / inorganic ➢ Moisture:

Why Additives? ▪ Wet: > 20 % humidity (i.e. suspension)

▪ Moisture: 3 – 20% Humidity
▪ Change in surface quality ▪ Dry: < 3% Humidity
▪ Dispersion of powders in suspensions
▪ Deformation caused by wear (metals!) ➢ Operation:
▪ Mechanical alloying ▪ Continuous
▪ Discontinuous
Powder Preparation - Background and Goals Preparation - Background and Goals

First question! How fine do you need your powder?

Powder preparation - Size reduction

Wet processing Moisture preparation Dry processing

> 25 % moisture 5-25 % moisture < 5 % moisture (bulk

(suspensions) (plastic masses) materials)

Examples: Examples: Examples:

Drum mill Pan grinder Vertical roller mill
Agitator ball mill (Attritor ) Sieve kneader Countercurrent jet mill
Powder preparation - Size reduction
Stress types during crushing Grinding by shear and abrasion

Initial grain size

Final grain size

Comminution by cleavage

Initial grain size

Final grain size

 Powder preparation - Wet preparation
Drum mill Dust extraction
Material feeding The degree of grinding in a ball mill is influenced by:
• Dwell time of the material in the mill chamber.
• Size and number of balls.
Material feeding
• The condition of the balls (hardness of the
material to be ground).
• Feed speed and filling level in the vessel.
• Rotation speed of the cylinder.

Grinding balls

Cascading movement Cataracting movement

Final product
Powder preparation - Wet preparation
Drum mill
Powder preparation - Wet preparation
Agitator ball mill (Attritor) Powder,
suspension agent

Stirrer

Grinding
balls
Powder preparation - Moist preparation
Edge mill

Material

Rollers

Grinding table
Grind
Motor
material
Powder preparation - Moist preparation
Clay shavers
Powder preparation - Powder

Particle shape
Powder preparation - particle size distribution
Powder preparation - particle size distribution
Since it is not always possible to provide diagrams and histograms, the best method is to give D10,
D50 and D90 of the powders. With these values (and a little expertise) it is possible to get a good idea
of the powder properties.
Powder preparation - particle size distribution
Unfortunately, the powders do not always show an "ideal" case, but a good analysis
provides valuable information.
Powder preparation - organic additives
How can we make a final product from powder?
Powder Organic additives are also required to produce
certain other properties of the slurry:

sinter additives

liquefiers - pH change, dispersion

dispersing agent - deagglomeration
wetting agent - surface tension
Further ingredients? defoamer - foam inhibitor

Solvent binder - mechanical stability of green body

plasticizer - flexibility (e.g. for film casting)
plasticizer - flexibility
abrasive - prevention of "sticking" to the mold (e.g.
for slip casting)
Production steps - Powder preparation
Necessity of colloidal processing??? We already know that since our childhood

For some
components we need
a better control
Powder preparation - organic additives

Agglomeration Dispergiermechanismus

electrostatic sterical elektrosterisch

dispersed Surface potential by pH osmotic pressure and Surface potential and steric effect by
Primary value adjustment (here "cushioning" by polymers with negatively charged
particles negative charges -) polymer molecules functional groups.
Powder preparation - organic additives

Example: Styrian stabilization of an Al2O3 suspension

+ Oleate solution
Produktionsschritte - Formgebung

Green Hard
Powder Processing Engineering Shaping sintering
processing processing
Shaping

forming
Press-
Processing:
Traditional

load
or complex
Number of items

forming
Plastic
Hot molding

Cold isostatic pressing

dispersing agent
(Wet-bag-pressing) Additive

Casting
manufacturing

Complexity of component shape

Uniaxial pressing

▪ Simple geometries e.g. substrates, bricks or tiles.

▪ Dry pressing also requires some organic additives to
increase tightness, reduce friction and facilitate
ejection.
▪ Also to reduce damage to the tools
▪ High stresses can cause large defects in the green
compact
▪ It can lead to inhomogeneous densities

▪ The deformation of the ceramic particles is very limited

(brittle), so that the maximum bulk density is ~ 60%.

▪ Simple and relatively simple geometries can be

produced
One side Double side
Slip casting

▪ Relative complex shapes!

▪ The thickness of the wall is constant! Typically, thin
thickness
▪ Excess of the suspension can be reused
▪ To facilitate the drying process, water content as low
as possible (25-35 wt.%)
▪ Low viscosity to increase the green density
▪ Green strength increases with increasing deflocculant
content
Slip casting
Slip casting - examples of application
Slip casting is used for the production of fine porcelain, washbasins, sanitary Barr
ware. formation in
case of two-
peaces form
Tape Casting

• Just tapes with thickness 25 µm to

1.5 cm
• Highly used in industry for SOCs,
electronics, capacitors, protection,
etc.
• Ceramic powders plus binders,
deflocculants and plasticizers.
Then, degassed slip, control of
thickness with doctor blade, and
continuous belt (protected with a
carrier polymeric film).
• Evaporation of solvent during
process
• More or less flexible depending on
binders.
Tape Casting
Tape casting - application examples
Tape casting is used for the production of multilayer ceramics for capacitors and dielectric insulators.

Aluminum nitride AlN

Multi-layer substrate
for storage elements.

Resistors
Capacitors
Extrusion

▪ Defined cross-sections as tubes of varying

complexity.
▪ "long" products
▪ Plastic behavior, control of rheology
▪ Feeding, metering screw and extrusion
Extrusion
Injection Moulding
▪ Common use for polymers and metals, less common
for ceramics

▪ Heavy use in industry due to the large number of parts

per time (a sample few seconds)

▪ Preparation of the starting material (ceramic powder

and additives)

▪ Complex shaped parts, thin wall thicknesses

▪ Multiple steps in production

Injection Moulding
Injection Moulding
Feedstock (powder binder granules) Injection molding

J. Am. Ceram. Soc., 99 [10] 3210-3213 (2016).

J. Gonzalez-Julian, et al.,
Kneter
62 vol.% Solids content Flow rate 15 cm3/s
23 vol.% Paraffin (Flow) 2h at 150 ºC Inj. Pressure 1150 bars
13 vol.% Hostalen (mechanical stability) Temperature 180 ºC
2 vol.% Fatty acid (lubrication) Form Temp. 90 ºC
Form Nozzle Heating element and screw
Feeding funnel

End binders Thermal debinding Sintering

Hexanes (paraffin) 2 K/min up to 500 ºC, 2h in Ar 5 K/min up to 1350 ºC, 5h, Vakuum
Injection molding

Sintered

Ø = 30 mm, Ra = 1.136 µm

▪ Shrinkage during sintering; this must be taken into account in the design of the component
▪ Good reproducibility and surface quality for the production of components with relatively
complex shapes
Injection Moulding – possible applications
Shaping

forming
Press-
Processing:
Traditional

load
or complex
Number of items

forming
Plastic
Hot molding

Cold isostatic pressing

dispersing agent
(Wet-bag-pressing) Additive

Casting
manufacturing

Complexity of component shape

Additive manufacturing of ceramics

▪ Some of the applications required really complex shapes

▪ Additionally, to the previous processes, new processes are required

A great future is here but more

progress in R&D is necessary to
improve materials and reduce costs.
Additive manufacturing of ceramics
Ceramic forming techniques
▪ Considerable increase of complexity

▪ Some components impossible by other processes Conventional methods

Slip casting Tapecasting Pressing

Hot molding Extrusion

Additive Manufacturing

▪ AM has opened another „world“ for ceramics Slurry-based Powder-based Solid-based

▪ But also, there is a hype, so think and evaluate! SL DLP IJP 3DP SLS LOM FDM

DIW TPP SLM

▪ Several different types, names and classification
Additive manufacturing of ceramics – classification

Feedstock Ceramic 3D printing technology Abb.

Slurry-based Stereolitography SLA

Digital light processing DLP
Two-photon polymerization TPP
Inject printing IJP
Direct inc writing (Robocasting) DIW

Powder-based Three-dimensional printing 3DP

Selective laser sintering SLS
Selective laser melting SLM

Solid-based Laminated object manufacturing LOM

Fused deposition modeling FDM
Additive manufacturing of ceramics – slurry-based methods

SLA DLP
Feedstock Ceramic 3D printing technology Abb.

Slurry-based Stereolitography SLA

Digital light processing DLP
TPP
Two-photon polymerization TPP IJP
Inject printing IJP
Direct ink writing (Robocasting) DIW

Powder-based Three-dimensional printing 3DP

Selective laser sintering SLS DIW
Selective laser melting SLM

Solid-based Laminated object manufacturing LOM

Fused deposition modeling FDM
Stereolithography (SLA)

Plattform Lichtquelle
▪ Stereolithography is one of the most attractive methods
due to the high quality of the finished parts.
▪ SLA enables production of objects with high surface
quality with fine resolution down to the micrometer range.
▪ The light-activated polimerization process is typically
activated by UV by scanning of the suspension surface.
When the polymerization of a layer is complete, the
platform is raised or lowered by the thickness of a layer
(depending on top-down or bottom-up application)
▪ The homogeneous dispersion of the ceramic particles and
the long-time stability (hours to days) of the
photopolymerizable suspension is crucial in the process to
obtain final products with good quality
▪ Viscosity, solids content and light refraction and
absorption by the particles affect the process significantly. Suspension of
▪ You are welcome to see SLA live in our 3Deramo Lab! monomeren und
keramischen Partikeln
Stereolithography (SLA)

Of particular importance is the difference in refractive index between the photopolymerizable medium and the
ceramic particles. Ceramic particles that exhibit greater light absorption and refraction when exposed to the
photopolymerization wavelength can be very difficult to process by SLA method.
Stereolithography (SLA)
Stereolithography (SLA)

Advanced ceramic parts fabricated using SiO2 via SLA: (a) porous bioceramic
scaffold; (b) photonic crystals; (c) hollow turbine blade; (d) impeller; (e)–(f):
investment casting moulds.
Chen et al. 2010

SiC parts prepared by SLA on pre-ceramic

polymers. Comparison of printed and sintered
samples (bottom)
(De Hazan et al. 2017)
Digital light processing (DLP)

▪ the method is similar to SLA and could be defined as a Platform

"mask-based SLA".
▪ an integral image is projected onto the
photopolymerizable liquid surface by exposing the light
source once through a defined mask.
▪ originally the masks were physically created, further
design - liquid crystal display (LCD) as a dynamic mask
generator.
▪ enable a significant shortening of the printing process -
much faster than the SLA dot line layer scanning
method.
▪ High surface quality and very good resolution, down to
several microns. Suspension of Transparent
▪ The higher efficiency of DLP compared to the monomeric and Vat
conventional SL process makes it a promising 3D ceramic particles
printing process for the production of ceramics.
▪ You are welcome to see LCD-DLP live in our 3Deramic Laser
Lab!
Two-photon polymerization (TPP)
▪ applied for nanoscale 3D structures in the fields of
nanobiomedicine, nanoelectronics and nanomechanics
▪ in this technique, polymerization is achieved by the
simultaneous absorption of two photons (TPA) of a
near-infrared (780 nm) or green (515 nm) laser in the
corresponding photosensitive resin inside the polymer
liquids and not on the surface, as is the case with LSA
or DLP.
▪ resolution in the submicron range

SEM images of various complex spiral microstructures fabricated by TPP technique. (Seet et al. 2005)
Inkjet printing

▪ the process is based on the principle of the well known 2D

printers, but here the individual suspension droplets are Plattform
precisely placed on top of each other to create the 3D
objects
▪ inks in which ceramic particles are well dispersed are
transferred to the print head and deposited directly and
selectively onto a substrate drop by drop. Computer-aided
high-precision positioning of the droplet jet enables a point-
line-layer build-up process
▪ possible problems: each applied layer must be dried
separately, stable suspension is required, rheological
properties important (printability), coffee stain effect, satellite
droplet formation
▪ advantages: production of multiphase or functionally
graded/graded parts possible by printing different ink
compositions. Printhead with
▪ You are welcome to see DIP live in our 3Deramic Lab! ceramic suspension
Inject printing

Si3N4-Gear manufactured by IJP:

(a) green part; (b) sintered part.

Cappi et al. 2008

Microarrays of columns: (a) PZT columns

with 1000 layers before sintering; (b)
4000 layers after printing; (c) TiO2
columns after sintering; (d) highly
magnified image of a column.

Bhatti et al. 2001

Lejeune et al. 2009
Direct ink writing (DWI / Robocasting)

Platform
▪ extrusion of a ceramic paste (or ink) through a small
nozzle (µm - mm).

▪ the rheology of the suspension is crucial, as it must

flow under pressure and have good mechanical
stability to withstand the new layer on the surface

nozzle
Direct ink writing (DWI / Robocasting)

▪ As mentioned the ink preparation is

determinant

▪ Shear thinning behavior (explained in other

lecture)

▪ Briefly, low viscosity at relative high shear

rate and high viscosity without any force.

Solids: 38 vol.% (76 wt.%)

Organics: 8.3 vol.% (PEI + MC + APA)
Ultrapure water: 53.7 vol.% Low viscosity at shear rate = 30-70 s-1
Low pressure extrusion
Direct ink writing (DWI / Robocasting)

▪ Filament shape retention

▪ Dry and burn-out without oxidation of the ▪ 24 layers/125 cells
ceramic
▪ Followed by sintering
Additive manufacturing of ceramics – powder-based methods
3DP
Feedstock Ceramic 3D printing technology Abb.

Slurry-based Stereolitography SLA

Digital light processing DLP
Two-photon polymerization TPP SLS
Inject printing IJP
Direct inc writing (Robocasting) DIW
SLM
Powder-based Three-dimensional printing 3DP
Selective laser sintering SLS
Selective laser melting SLM

Solid-based Laminated object manufacturing LOM

Fused deposition modeling FDM
Three-dimensional printing (3DP)

▪ powder-based process in which an organic, liquid binder Powder

is applied to a powder layer in a computer-controlled
targeted manner by a spinning head. The platform with
the object is then lowered by one layer thickness and
simultaneously pushed up in the container next to it. The
protruding powder is transferred to the platform with the
part to be printed and again selectively treated with the
organic binder. Layer by layer, a part is then created.
▪ suitable rheological properties (surface tension and
viscosity) are needed for the binder solution to be ejected
through the print heads.
▪ sintering is required to remove the organic binder and
achieve final mechanical stability.
Platform
▪ resolution of the printed parts depends on the size and Printhead with
shape of the powder and the properties of the binder. binder
Three-dimensional printing (3DP)
 Selective laser sintering (SLS) und Selective laser melting (SLM)
Laser SLM
▪ similar to SLS
▪ here complete melting of the powder to a solid part by
high-energy laser scanning layer by layer, without
binder
▪ subsequent sintering not necessary (ready-to-use
ceramic parts)
Powder
High-energy laser
Platform
SLS
▪ similar to 3DP, but instead of binder, a high-power laser
beam is used to solidify the component.
▪ organic (polymers) or inorganic (low-melting metal- Powder
based materials and glass) binders are used in the
process
▪ sintering required to eliminate the binder components
▪ high shrinkage and high porosity Platform
 Selective laser sintering (SLS) und Selective laser melting (SLM)

(a) complex 3D cellular models;

(b) final porous structures
fabricated with SLS; (c) 3D model
of a human bone (d) final scaffold
fabricated with SLS; (e) SEM
image of a layer of the fabricated
scaffold; (f) cytocompatibility
testing.

Duan et al. 2010

Surface morphology of the

sintered ZrO2 object with the
following features: (a) cracks; (b)
open pores; (c) ZrO2 objects
produced by SLM.

Shishkovsky et al. 2007

Additive Fertigung von Keramiken - Feststoff-basierend

LOM
Feedstock Ceramic 3D printing technology Abb.

Slurry-based Stereolitography SLA

Digital light processing DLP
Two-photon polymerization TPP
Inject printing IJP
Direct inc writing (Robocasting) DIW

Powder-based Three-dimensional printing 3DP FDM

Selective laser sintering SLS
Selective laser melting SLM

Solid-based Laminated object manufacturing LOM

Fused deposition modeling FDM
Laminated object manufacturing – LOM
▪ computer-controlled laser cutting of prepared thin Platform Laser cutter
ceramic foils according to CAD models and
subsequent placement of single layers on top of each Role
Tape-casted
other by controlling the platform. The foil can be
green ceramic
activated on the surface to ensure good adhesion
between layers.
▪ the advantages of this technique are: the elimination
of distortion and deformation due to the low thermal
stresses generated during the manufacturing process.
▪ problems that can occur: delamination, pores in layer
interfaces, anisotropy.

Travitzky et al. 2008

Rodrigues et al. 2000

Ceramic components fabricated with LOM: (a) turbine rotor made of Al2O3; (b) SiC gears; (c) complex shaped Si3N4 parts.
Fused deposition modeling (FDM)
Filament
▪ the filament (ceramic powder + thermoplastic binder)
is continuously fed to a moving nozzle and heated
therein to a temperature just above its melting point
so that it can be easily extruded through the nozzle
to form layers. After extrusion, the material solidifies
immediately
▪ final bonding and sintering are required after the
process
▪ important factors: the size/distribution and dispersity
of the ceramic particles in the filaments, the
ceramic/binder/additive ratio, and the viscosity and
thus flexibility of the filaments after heating.

Nozzle
Fused deposition modeling (FDM)

Fine structures manufatcured by FDM (Yang et al. 2006)

(a) kneaded feedstock; (b) composite filament (Khatri et al. 2018)

Bioceramic scaffolds manufactured by FDM (XU et al. 2008, Chen et al. 2001)
Additive manufacturing of ceramics at one glance

Feedstock Ceramic 3D printing technology Abb. Forming Power source Post-treatement Speed

Slurry- Stereolitography SLA Polimerizatin Laser Debinding/sintering Slow

based Digital light processing DLP Polimerization Laser Debinding/sintering Medium
Two-photon polymerization TPP Polimerization Laser Debinding/sintering Slow
Inject printing IJP Binder Thermal energy Debinding/sintering Slow
Direct inc writing (Robocasting) DIW Extrusiom Thermal energy Debinding/sintering Medium

Powder- Three-dimensional printing 3DP Binder Thermal energy Debinding/sintering Medium

based Selective laser sintering SLS Powder fusion Laser Debinding/sintering Medium
Selective laser melting SLM Powder fusion Laser No post-treatment Medium

Solid- Laminated object manufacturing LOM Sheet lamination Laser Debinding/sintering High
based Fused deposition modeling FDM Extrusion Thermal energy Debinding/sintering Medium