Allgemeine Prozesstechnik (APT)

Overview of ceramics and energy consumption

Prof. Jesus Gonzalez-Julian

Institut für Gesteinshüttenkunde (GHI); Chair of Ceramics
Organization

Prof. Jesus Gonzalez-Julian ([email protected])

Chair of Ceramics at GHI

New Professor, new activities and lectures

Index of the ceramic lectures

Overview of ceramics and energy consumption

Synthesis and milling

Exercises (Übungen)

Processing/Additive manufacturing

Sintering

Exercises
Index of introduction

Overview of ceramics

Classification

Energy consumption

Performance

Energy transition and circular economy

Summary
Overview of ceramics

Can you define ceramics? Main characteristics, compositions…

How much energy is consumed during the processing of ceramics? Which are the
steps that require more energy?

Do they play a role in the energy transition (Energiewende)?

Overview of ceramics

Natural (paper, wood, etc.) and synthetic materials

Final products made of synthetic materials: for example wires

Plastic Metal Ceramic

• Light • Flexible • Why not?

• Cheap • Cheap • A ceramic wire?
• Flexible • Durable
Overview of ceramics
Increasing the complexity…now a tube

Plastic Metal Ceramic

• Light • „Flexible“ with • Rigid at room and high temperature
• Cheap Temperature • Relative expensive (why?)
• Flexible if • Cheap • Durable and harsh environments
desired
We are scientists & engineers !!!! Full analysis, evaluation and understanding

Different materials mean different properties; materials according to the applications

Overview of ceramics

Ceramic processing… no pain no glory!

Forging Melting and shaping Ductility / rolling Easy machining

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

Ceramics cannot be forged, melted and shaped, they are not ductile and difficult to machine
Overview of ceramics

Ceramic processing
Produce a final dense ceramic component is a complex task that is based on some steps

Synthesis / mining Produce a green body Consolidation Polishing and

of powders (moulding, shaping) (sintering) machining

 Natural or artificial  Critical step  Critical step  Optional

 Shape  Green body: shape  Thermal treatment  Surface treatment
 Size of the ceramic below melting  Machining is
 Purity before sintering  Different methods complex due to
 Defects  Several techniques:  Several parameters hardness and
 Controlled by dry, suspensions,  Different stages brittleness
method deposition, etc.  Shrinkage  Time and cost
 Packing/porosity  Control of microstructure
and properties
Overview of ceramics

Synthesis / mining Produce a green body Consolidation Polishing and

of powders (moulding, shaping) (sintering) machining

Energy situation
Huge role of ceramics

Mining: location, political conflicts, etc.

Processing of green body and sintering

(high temperatures; typically > 1000 °C)
consume a lot of energy
Energy consumption must be
strongly reduced…but then we
need to understand and analyze
Overview of ceramics

Different materials means different responses.

The selection depends on several factors Nanomaterials

Environment, temperature, pressure, forces, Polymers

costs, appearance, availability, weight, etc. and metals

But interest and reputation are not always fair Materials

science
Nanomaterials: future, electronics, etc

Polymers: Flexibility

Metals: functionality, Hard (What?!)

Ceramics: Potery, bricks and toilets

Ceramics
Overview of ceramics

Porcelain, potery, toilets

Biomaterials, drug-delivery, tumor

detection, space vehicles, energy
transition, solar panels, concentrated
solar power, safer Li-batteries, H2-
corrosion protection, superconductors,
microchips, formula-1 components, space
exploration, buildings in Mars, highly
efficient engines, and …. yes nice cups
Overview of ceramics

Why are ceramics difficult to process?

 The chemical bonding

 The high melting temperature (even in some cases > 3000 °C – UHTCs)

 High elastic Modulus and brittle (related to chemical bonding)

 Shrinkage during sintering

Overview of ceramics

Ceramics are inorganic, solid and non-metallic materials that are

insolvable in water and are at least 30 % crystalline.

Crystallinity: degree of structural order in a solid. Long range  ceramics, short range  glasses
Important: salts (soluble in water) and glasses (< 30% crystalline)

They are usually moulded at room temperature from a raw material mass, followed by a
temperature treatment (which is called SINTERING) at above 800°C to consolidate the material.
As a consequence of the thermal treatment, a specific microstructure is developed, which will
determine some of the properties.

*In some cases moulding may also occur at higher temperature or by smelt casting with
subsequent crystallisation.
** Some properties are determined by the composition (density, melting point) and others by the
microstructure (mechanical, thermal, electrical properties).
Classification

Ceramics

Technical ceramics Advanced Ceramics

(Traditional Ceramics) (High-Tech, Fine Ceramics)

Refractories
Functional Ceramics Structural Ceramics Bio-Ceramics
Chemical porcelain
Electro and thermal High strength, Bioinert,
Construction response toughness, melting bioactive, and
point, thermal shock, bioresorbable
Insulators reliability
Classification
Classification: According to chemical composition or „family“ of materials
Oxide ceramics: Carbides:

Alumina Al2O3 Boron carbide B4C

Zirconia ZrO2 Silicon carbide SiC
Magnesia MgO Titanium carbide TiC
Spinel MgAl2O4 Tungsten carbide WC
Mullite 3Al2O32SiO2
Barium titanate BaTiO3 Borides:

Nitride ceramics: Titanium diboride TiB2

Zirconium diboride ZrB2
Silicon nitride Si3N4
Aluminium nitride AlN Silicides:
Titanium nitride TiN
Titanium disilicide TiSi2
Molybdenum disilicide MoSi2
Classification
Classification: According to chemical composition or „family“ of materials
MAX phases: layered ternary carbides and nitrides

A-A Ti3SiC2
(Metallic)
M-X Cr2AlC
(Carbide or
nitride) Ti2AlC
A-A
(Metallic) Ti3AlC2
M-X Nb2AlC
 Characteristic layered A-A Ti2AlN
microstructure …. (>150)
M-X
 > 150 different compounds;
A-A
and solid solutions 500 nm
Covalent/ionic/metallic
Classification
Classification: According to chemical composition or „family“ of materials

UHTCs: Ultra-High Temperature Ceramics

More than 300 materials with melting temperatures over 2000 C,

but just a few with > 3000 °C

Borides, Carbides and Nitrides (quite interesting properties)

NUCLEAR APPLICATIONS HYPERSONIC APPLICATIONS

High potential and expectations

Some limitations so the approach is to

develop ceramic matrix composites
Classification

The composition defines some properties but not all of them!

Allotropes, microstructures, macrostructures, grain boundaries, secondary phases

How a ceramic is processed is determinant

Classification

Alumina (Al2O3) is one of the most used ceramic compounds

Different phases and stability

Solid solutions (mullite 3Al2O3:2SiO2), doping (precious

gemstones)

Doping:
Fe, Ti, Mg, V…
Classification
Zirconia (ZrO2) is also one of the most studied ceramic and structural material

Different phases (and properties) with a volumen change!

It is typically stabilized
Classification

Classical Porcelain Composition

Raw Materials: natural (minerals),

Kaolinite 50 % (25-65 %)
Feldspar 25 % (20-40 %) almost exclusively silicates
Quartz 25 % (10-40 %) mechanically less processed
+ Water
with natural impurities

Examples: SiO2 Quartz

NaAlSi3O8 Sodium feldspar
KAlSi3O8 Potassium feldspar
CaAl2Si2O8 Lime feldspar
Al4[(OH)8Si4O10] Kaolinite
Ca0.2[Al1.5Fe0.3Mg0.2(OH)2][Si3.75 Al0.25O10]
Montmorillonite
Classification

Kaolin / Clay = Mix of layered silicates

Type of layer silicates, grain size
and blending ratio control

- mouldability
- colour of product
- strength
- prize

Al4[(OH)8Si4O10]
(Kaolinite)
Classification

Traditional Ceramics = Silicate ceramics

Easy!
Approx. 90 % of
Earth's crust

We use that we have!

In Mars? If we want to colonize it
we need to use its resources
Classification

Coarse ceramics Fine ceramics

visible microstructure without visible microstructure

Construction Materials (bricks/roof tiles) Tableware and sanitaryware (porcelain, stoneware)

Waste water tubes (stoneware) Insulators (porcelain)
Floor tiles (stoneware...) Chemical ceramics (porcelain, stoneware)
Arts (terracotta, porcelain...)
Markets and Costs
Markets and Costs *Exception: Tableware, arts

Cheap raw mat.: 1000 kg = 10-20 € raw materials: 1000 kg = 100-200 €

High output rate: >50 Mio tiles/year/plant low production rate: 1-10.000 pieces/year/plant
Low gain in value: 1,20 €/tile high gain in value: 5-50…>1000 €/piece
High energy costs: drying/firing high energy costs: drying/firing
High personel costs high personel costs
Unstable quality constant quality by repair
Classification
Automation in Silicate Ceramics Technology

Clay mining around 1950 Nowadays All fields need an update

to be competitive and
increase efficiency

Continuous process
Classification

Roof tiles Bricks Tiles

Energy Strength Other functionalities (heating)

Classification

Technical Ceramics – Porcelain and construction

Weight

Less material
Why do bricks have holes?
Less heat during processing!!!

Cheaper (transport, production and materials)

Classification
A bit of history is needed….

Materials science has been from the beginning to survive and progress

First materials were (and still are) natural: stones, wood, bones, skin, etc.

Ceramics were the first synthetic material, being a technical heritage of mankind

Needs of the time: collecting water, housing, production of other materials and decoration (!!!!)

WHY?

Ganges
Classification

Figure/religion/decoration Conservation and transportation of food

Venus of Sudan, 8000 B.C.

Dolni Vestonice,
Tschechia

first known fired

and glazed
ceramic body

Halaf-Period, Iraque, 4500 B.C.

Multi-coloured glazing

25th Mill.B.C.
Classification

Housing/architecture

Pyramid of Djoser, Saqqara, Egipt, approx. 2670–2650 BC

No this picture!!!!!
But sun-dried bricks for
houses and ovens (foods) and
later other materials

Mohenjo Daro, Harappa; Indus

culture, 4th-3rd Mill.B.C.
Classification

Daylife activities

First Written Accounts Encarved in Moist Clay

First Data File
Classification

Processing

It looks easy but it isn´t

They were really experts

Egypt: Mass production of ceramics since 4th-3rd Mill.B.C.

Classification

Töpferscheibe Freihand-
Formgebung

Brennöfen

Trocknung
Classification
Casting of metals

Principle of Bronze Casting: Wax Moulding and Smelting

Classification
Casting of metals

Roman Brass Smelting Crucible with Residues

of Copper and Zink Ores; Neuss, 23-45 A.D. Ceramic Moulds for Bronze Casting, Shanghai Museum
Classification

Ovens

Large-scale kilns („dragon kilns“) Firing capsules for seladonian-porcelain in

China, since 1700 B.C. industrial scale; China, since 1200 B.C.
Energy consumption

Ceramic processing
Produce a final dense ceramic component is a complex task that is based on some steps

Synthesis / mining Produce a green body Consolidation Polishing and

of powders (moulding, shaping) (sintering) machining

 Natural or artificial  Critical step  Critical step  Optional

 Shape  Green body: shape  Thermal treatment  Surface treatment
 Size of the ceramic below melting  Machining is
 Purity before sintering  Different methods complex due to
 Defects  Several techniques:  Several parameters hardness and
 Controlled by dry, suspensions,  Different stages brittleness
method deposition, etc.  Shrinkage  Time and cost
 Packing/porosity  Control of microstructure
and properties
Energy consumption

Synthesis / mining Produce a green body Consolidation Polishing and

of powders (moulding, shaping) (sintering) machining

Green body: It is the shape of the ceramic before the thermal treatment for the consolidation. The
shape should be close to the final product because machining of ceramics is difficult. At this stage the
ceramic particles (powders) are weakly bonded. It is common to use additives to form the green body.

There are several techniques to produce

green bodies: from slip casting to additive
manufacturing techniques.

And practica in the lab with 3D printing soon!

Energy consumption

Processing of ceramics: traditional or advanced

 From particles to a desired shape (reminder!: no forging, melting or –practically cutting/machining-)

 Addition of water and additives such as binders, lubricants, etc. to form a paste/suspension/ink/etc.

 Following to a shape forming process

 Obviously, control of amount and

composition of these additives. Typically,
as less as possible

 They depend on the processing technique

Energy consumption

Processing of ceramics: traditional or advanced

New complexity level

impossible until now

AM
Energy consumption

 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

Energy consumption

Additive Manufacturing of Ceramics

 Considerable increase of complexity

 Some components impossible by other processes

 AM has opened another „world“ for ceramics

 But also, there is a hype, so think and evaluate!

 Several different types, names and classification

Energy consumption

Synthesis / mining Produce a green body Consolidation Polishing and

of powders (moulding, shaping) (sintering) machining

Sintering: thermal process (might be assisted by pressure) to consolidate a powder compact into a
ceramic solid mass. Sintering is driving by the reduction or the energy of the system and it typically
implies a reduction of the porosity and consequently, a shrinkage of the body. The sintering process
defines the microstructure and consequently the properties of the ceramic material.
* Typically oven to consolidate pottery, but there
Several parameters play a role during are much more such as Spark Plasma Sintering
the densification such as heating rate,
maximal temperature, dwell time,
atmosphere, etc.

Several techniques and novel

methods to develop new materials!
More in the next lectures
Energy consumption

High temperatures (> 1000 °C), slow heating rates (~ 10-20 K/min) and long
isothermal holding times (hours)

Microstructural evolution during firing of powder particles

Energy consumption

100 Intermediate phase

Relative density (%) Final phase

Powder

Starting phase

50

Temperature (ºC) Isothermal holding time (min)

Powder Starting phase Intermediate phase Final phase
Particles are Formation of sintering necks Maximal sintering rate Reduction of the
only in contact Reduction of the surface energy porosity and grain
Reduction of the porosity
Grain boundaries between the particles growth
Energy consumption
 Today it is not about sintering but it is of course an importance step
 „Conventional“ sintering is absolutely determinant (most of the products) but new
techniques are essential to reduce the energy consumption (low temp and shorter times)
Spark Plasma Sintering

 DC pulse current process

 Assisted by uniaxial pressure
 Controlled atmosphere
 High heating rates (> 100 °C/min)
Max. temp. 2200 °C
 Short dwell time (min)
 Limited grain growth

More in a few days and soon in our institute!

Energy consumption
Functionally Graded Materials (FGM) Transparent ceramics

Nanostructured Materials
ZnO Si3N4/CNTs
Composites

200 nm 500 nm

Joining Metal/ceramic Cr2AlC Novel materials

20 µm 5 µm
Performance

 Processing: to shape (give a form) of the green body

 Sintering: to densify the ceramic compound

Good! But, are all the samples equal? Same microstructure?

Defects?

Defects in ceramics are really important and they are

„incorporated“/“produced“ during the processing and sintering,
but mostly processing
Defect size - Processing
Defect size - Processing
Fracture toughness
Strength (Festigkeit)
The first step to increase the toughness and strength is
the reduction of the defect size (c). This is achieved 𝐾1𝐶
𝜎𝑐 =
through the processing (synthesis, green body, 𝜋𝑐𝑐
sintering) of the ceramic compound
Defect size

c
Defect size - Processing

2a
2c

Pore in SiC Abnormal grain growth in Al2O3

2a

Residues in ZrO2 Organic inclusions in Al2O3

Performance
Performance

Risk

Proof-Test

Optimization of the material

Performance

Keramisches Denken

"Ceramic" is not just a class of material, but a process chain!

Energy Transition & Circular economy

Certainly, this topic is really wide and I will explain it in a single lecture (new semesters)

Here just a brief info about that…some of this will be done in the ceramic chair.

Energy transition (Energiewende)

Ceramics will participate in most of the

different fields to increase the efficiency
and protect materials. Impossible in a single
lecture (it is a whole master)

…solar panels, concentrated solar power,

safer Li-, Na-batteries, H2-corrosion
protection, catalysis, etc.
Energy Transition & Circular economy

Electronics
Energy Transition & Circular economy
Energy Transition & Circular economy

Space exploration

From protection of spacecrafts, and

magnetic, electric and radiation shielding

…to mining and buildings in Mars (regolith)

Energy Transition & Circular economy

And of course much much more

Biomaterials, drug-delivery, tumor detection, biomedicine

Sustainability and circular economy

Novel functionalities by bio-inspired materials

Additive manufacturing (lab for students soon!)

Transparent ceramics for communication

Sensors and actuators

Novel refractories

Aggressive environments etc.

Energy Transition & Circular economy
Energy Transition & Circular economy
Energy Transition & Circular economy

Current situation of the ceramic field

 Acquiring world leadership in waste-based ceramic materials. The use of at least 85% recycled materials
strengthens the waste market, which helps preserve natural stocks of virgin and important minerals such as
clays, limestone and feldspar and reduces imports of minerals such as zirconia, bauxite and magnesia.
 Widening the market for more sustainable ceramic products to replace other materials such as concrete,
granite and marble.
 Reducing in the energy consumption of the milling and firing processes (electricity and methane are the
highest factors of impact on the production cost of tile);
 Improving health in the workplace thanks to the lower amount of free crystalline silica in the ceramic body.
Energy Transition & Circular economy

Current and future direction

Additive manufactuing of houses (in earth

but also in other planets)
Reduction of energy, transport, safety, etc.

Novel materials (more enviromentally

friendy, reused, alternative fibers, etc.)
Energy Transition & Circular economy

Current and future direction

Summary

 The ionic and covalent bonding of ceramics entails good properties such as high elastic
modulus or melting point, but limits the processing. The ceramic processing is relative
complex but determinant to control the final properties of the component.

 Processing and sintering (high temp and long times) of ceramic compounds consume a
considerable amount of energy, so alternative methods (i.e. additive manufacturing or
advanced sintering techniques) are required.

 Circular economy is totally required in the ceramic field – as in other fields – to reduce the
energy consumption, mining, waste and usage of materials. It has to be tackled in
different directions from processing to applications.

As mentioned, new chair and lectures, so please give me your opinion

[email protected]