Willkommen zu Vorlesung: Keramische Werkstoffe - Prof. Dr. Alexander Michaelis Professur für Anorganisch-Nichtmetallische Werkstoffe - TU Dresden
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Willkommen zu Vorlesung:
Keramische Werkstoffe
Prof. Dr. Alexander Michaelis
Professur für Anorganisch-Nichtmetallische Werkstoffe
© Fraunhofer IKTSFakultät Maschinenwesen Institut für Werkstoffwissenschaft, Professur für Anorganisch-Nichtmetallische Werkstoffe Keramische Werkstoffe (anorganisch-nichtmetallische Hochleistungswerkstoffe) Definitionen und Abgrenzungen: Silikatkeramik / Hochleistungskeramik / Struktur- Funktionskeramik Chemische Bindung und Struktur / typische Werkstoffklassen (Oxid- , Nichtoxidkeramik) Mechanische Eigenschaften: Griffith, Weibull, Verstärkunsmechanismen, Kriechen, SCG, Thermoschock, Thermische Eigenschaften Herstellverfahren Strukturkeramik (Pulversynthese, Masseaufbereitung, Formgebung, Entbindern, Sintern, Endbearbeitung) Sintern Herstellverfahren Funktionskeramik (Dickschicht, LTCC, HTCC), Additive Manufacturing Dielektrika, Piezo- Pyro.- Ferroelektrika, Keramische Systeme: Kondensatoren /Dielektrika für die Halbleitertechnologie Brennstoffzellen, Lambda Sonde Keramik für Umwelttechnologie 2 © Fraunhofer IKTS
300 years of advanced ceramics in Dresden
Johann Friedrich Böttger
* 1682 in Schleiz; Ehrenfried Walther von Tschirnhaus
† 1719 in Dresden * 1651 in Kieslingswalde
† 1708 in Dresden
3 © Fraunhofer IKTSWas ist Keramik? Geschichte
Alt-Steinzeit
Älteste Tonfiguren
vor ca. 2000 Jahren
China - Herstellung von erstem Porzellan aus
„besonderen Tonvorkommen“
1709
Entwicklung des ersten europäischen Hart-Porzellans durch
Böttger und Tschirnhaus in Dresden, Meißen – erste gezielte
Werkstoffentwicklung
1849
Einsatz von Isolatoren aus Porzellan durch Werner von
Siemens für Telegrafenleitung von Frankfurt nach Berlin
1931
Firma Hanke und Siemens: Sinterkorund-Zündkerze; erstmalig synthetischer
Rohstoff für die Herstellung Technischer Keramik eingesetzt
50-er Jahre
Durchbruch für synthetische keramische Werkstoffe
70-er Jahre
Durchbruch für Funktionskeramik (Elektrotechnik, Elektronik)
80-er Jahre
Keramikeuphorie: „PKW-Gasturbine“, „Keramikmotor“
umfangreiche Forschungsaktivitäten
4 © Fraunhofer IKTSKeramik:
“Mineralien unterschiedlicher Zusammensetzung und
zweifelhafter Reinheit werden einer schlecht meßbaren
Wärmebehandlung ausgesetzt, die lange genug dauert,
um eine unbekannte Reaktion unvollständig ablaufen zu
lassen, wobei sich heterogene nichtstöchiometrische
Verbindungen bilden, die als Keramik bekannt sind”.
Keramik: Anorganisch, Nichtmetallischer Werkstoff
5 © Fraunhofer IKTSAssociations with ceramic 6 © Fraunhofer IKTS
Associations with ceramic 7 © Fraunhofer IKTS
Associations with ceramics ?
Keramik ist oft im System integriert und nicht sichtbar:
Erfüllt aber die Schlüsselfunktion
8 © Fraunhofer IKTS
Ceramtec; Doceram; Ibiden, Rauschert, IKTS; TASKCeramtec Associations with ceramic? 9 © Fraunhofer IKTS
Einzigartige Eigenschaften von Keramik:
» Sehr Hart und Formstabil
Maschinenbau
» Korrosions- und Verschleißfest
Automobilbau
» Hochtemperaturbeständig
Energie Systeme
» Leicht
» Biokompatibel LifeScience / Gesundheit
» Multi-Funktional IT / Elektronik
(„alle“ phys. / chem.
Eigenschaften möglich)
- Aufgrund der Eigenschaftsvielfalt haben Keramiken ein enormes Potenzial für
Produktinnovationen
- Die technologischen Möglichkeiten sind noch weitgehend unausgeschöpft
Große F&E Anstrengungen notwendig
- Keramische Werkstoffe bestimmen die Grenzen der Technik!!
10 © Fraunhofer IKTSSpannungs-Dehnungsverhalten verschiedener
Werkstoffgruppen / K1C Anpassung (Fasern)
11 © Fraunhofer IKTSGriffith behavior
K IC
σf ≈
The strength of a brittle material depends on the
fracture toughness and the largest defect size in
c the loaded volume
Depend on microstructure
Depends on the technology
- Pores
-Inclusions
-Cracks
-Large grains
© Fraunhofer IKTSFraunhofer Institute of Ceramic Technologies and Systems IKTS, Germany
Core Competencies
Structural ceramics Functional ceramics
Materials Sintering / Materials - Energy systems TEG
Diagnostics and NDE (non and life science
destructive evaluation)
Processes and Environmental Electronics / Smart Microsystems
Components Engineering
Additive Manufacturing Industry 4.0
13
© FraunhoferClosed techonolgy chains: structural ceramics
1 powder processing 2 shaping
3 firing 4 finishing
14 © Fraunhofer IKTSHigh Performance Aluminium and Zirconium Oxide
Ceramics for Medical and Sensor Applications
Optimized microstructure (uniform sub-micrometer grains, reinforcement with secondary
ceramic phase, enhanced density)
Improved mechanical properties (flexural strength, fracture toughness, micro-hardness,
enhancement by factor 1.5)
200 nm
REM photograph of an Surface toughened High dense Al2O3 Ceramic tooth crown
etched Al2O3 ceramic Al2O3 joint implant pressure sensor (ZrO2)
surface membranes
15 © Fraunhofer IKTSVeranstaltung Reaching physical limits
Vortragstitel Ort, Datum
IKTS-Mosaik-window
81 ceramic-tiles
© Fraunhofer
16Fraunhofer IKTS
Polycrystalline Ceramic
Very hard (equivalent to sapphire) scratch resistant
Excellent in-line transparency (at any thickness, any background)
Example (by IKTS): Real in-line transmission ~83%
(at 4 mm thickness)
Discs in photos: 4 mm thick, 0.6 µm grain size, hardness
HV10 ~ 14.5 GPa
(A. Krell et al., Int. J. Appl. Ceram. Technol. 2011, 1108-1114; Opt.
Mater. 2014, 61-74)
ceramic: scratchproof as sapphire, but not as prone to cracks
© FraunhoferSmart transparent ceramics in the Int. Year of Light
Ceramic Coverters for laser-LED- head lightning
Improved life time
Improved luminosity and heat dissipation
Improved down conversion
Different light colors
Lower production cost
© FraunhoferCore competencies: Fraunhofer Institute of Ceramic Technologies and Systems IKTS
Structural ceramics Functional ceramics
Materials Sintering / Materials - Energy systems TEG
Diagnostics and NDE (non and life science
destructive evaluation)
Processes and Environmental Electronics / Smart Microsystems
Components Engineering
Additive Manufacturing Industry 4.0
19
© FraunhoferTechnology platform functional ceramics
Functional ceramics
1 Paste / ink preparation 2 tape casting, printing
Energy systems TEG
and life science
3 3D-stacking 4 Lamination / sintering
Electronics / Smart Microsystems
Industry 4.0
20 © Fraunhofer IKTSMultifunctional materials
Cost barrier for economic
Production costs for components
success
Functions
© FraunhoferProduction technology platform MLC (LTCC/HTCC) © Ceramtec AG 22 © Fraunhofer
Low Temperature Cofired Ceramics (LTCC)
Cutting
Via-Punching
Via-Filling
Screen Printing
Collating
Laminating
Pressure
23 © Fraunhofer IKTSCeramic Microsystems – LTCC micro hybrid
Requirement for high acceleration / temperature
temperature up to 240 °C
acceleration up to 30g
gear box control EM19
with 32-bit micro hybrid ECU
© Fraunhofer IKTSLTCC – 3D Integration: multi layer ceramic technology
Technology steps for the fabrication of LTCC-based pressure sensors
- Punching
- Via-filling/ screen printing I
- Laminating I
- Laser ablation/ cutting
- Laminating II
- Firing
- Screen printing II
- Firing
Coexistence of electronic and fluidic components
© FraunhoferSensor and actuator development
physical
Mechanic (p, a > 100.000 g, F) Flow Temperature
chemical
pH, Ion-concentration Gases / CO2 Humidity
26 Dickschicht- und Multilayer-basierte keramische Sensoren und Mikrosysteme
uwe.partsch@ikts.fraunhofer.de
© Fraunhofer IKTSSENSOR AND ACTUATOR SYSTEMS FOR HARSH ENVIRONMENTS! INDUSTRY 4.0 eHarsh Quelle: mcucoatings.com Quelle: flickriver.com Quelle: Rolls-Royce plc Quelle: seniorflexonics.de Quelle: momentum-magazin.de Quelle: energy-mag.com Quelle: IPT Quelle: faz.net 27 © Fraunhofer
Additive Manufacturing of ceramic 2,5D and 3D-components
Funktionskeramik Strukturkeramik
Ceramic Multilayer Printing + Ceramic Injection Moulding
(CIM)
= Additive Manufacturing
Technology / LTCC
Porous + dense
porous
dense
© Fraunhofer IKTS © LITHOZ GmbH
3D
2.5D 3D
Lateral resolution 50µm
Min. lateral resolution Lateral resolution 100µm
30µm Multi-material Systems
Multi-material Systems
Multi-material (e.g. 2-component Functionalization
-integration moulding) Co-Sintering
Materials Know How
28Energy and Environmental Technology at IKTS
Ceramics for combustion Membranes for Filtration Fuel Cells
engines and turbines Oxyfuel / Power to Gas
Renewables Energy Harvesting Storage Technology
(Piezoceramics, TEG)
Li-Battery
Supercup
Na-NiCl
SOEC -
(Electrolysis)
© Fraunhofer IKTSThe American Ceramic Society`s 2015 Corporation
Environmental Achievement Award
Ceramic nanofiltration membranes for efficient water
treatment
Industrial waste water
treatment unit
Winners of the last years: Murata Electronics, Toyota Central Research,
OSRAM SYLVANIA Products, Pilkington Technology Management
Limited, SCHOTT North America
© Fraunhofer IKTSProduced water treatment with ceramic nano filtration
membranes
“Produced water”: byproduct in oil and gas industry
(water flooding of oil reservoirs to increase yield, oil sand refinery, fracking)
Challenges: ingredients of „produced water“
Particles (abrasion)
Oil and tar (high fouling)
Salts (high scaling)
Results: Ceramic membranes
Separation of oil droplets by microfiltration
Feed
Partial desalination by nanofiltration
Both together with one step nanofiltration
Ceramic membranes Retentate Permeate
© Fraunhofer IKTSStructure of ceramic
membranes
Environmental and Process Engineering
Ceramic Membrane Materials
Ceramic Membranes
Amorphous MIECs
R-O O-R
Me
R-O O-R
R-O O O-R Me
Me
R-O O O-R
R-O O-R Me Zeolites Carbon
R-O O-R
32
© FraunhoferEnvironmental and Process Engineering
Examples of Application
Ceramic Membranes
Amorphous MIECs
Zeolites Carbon
Biogas Oxygen separation
purification
Wast water
cleaning
Bioethanol
dewatering
33
© FraunhoferEnergy and Environmental Technology at IKTS
Ceramics for combustion Membranes for Filtration Fuel Cells
engines and turbines Oxyfuel / Power to Gas
Photovoltaics Energy Harvesting Storage Technology
(Piezoceramics, TEG)
Li-Battery
Supercup
Na-NiCl
SOEC -
(Electrolysis)
© Fraunhofer IKTSThe Energy future – as we see it
conventional
Biogas
Power generation PtG
technology
SOFC MCFC
Range Solar Solar Wind
extender
SOFC
technology
Storage
SOEC
Supercap Li-Ion NaNiCl Redox-Flow Power
to Gas (Fuel)
Small grid Grid
residential commercial Industry 6 .. 7 Base load
Scale
e-mobility Application
kWh TWh
approaching real decentralized (no-grid) solutions
© FraunhoferLi-Ion Battery value chain
Electrode Cell assembly &
Powder synthesis Slurry Mixing Cell testing
manufacturing packaging
Powder synthesis Development of Efficient Material and Electrical and
and modification an adapted slip methods for electrode thermal
Methods for compositions slurry mixing characterization characterization
analysis and for the coating Development of Sophisticated of commercial
optimization of process technologies for spectro- cells
thermal process Sophisticated coating of electrochemical Stationary and
Methods for methods of electrode films characterization dynamic
characterization slurry (impedance, modeling of
of powders characterization Raman,…) battery cell
(FESEM, XRD; and performance
Raman; thermal optimization
properties;
particle size )
© Fraunhofer IKTSCeramic Materials and powder processing dertermines battery
performance Makro- to Nano evaluation
Tap density
Capacity Discharge current
Processing Cycle stabilty
Power density
Life time
Safety
37 © Fraunhofer IKTSExample: Electromobility
Tesla Model S
Ca. 500 km Reichweite
96 Zellen
je 60 Ah
~ 8000 Zellen
je 3,4 Ah
BMW i3
150 km Reichweite
© Fraunhofer IKTS - 38 -LiNi0,5Mn1,5O4/Li4Ti5O12 – Bipolar battery
© Fraunhofer IKTS
VERTRAULICH
- 39 -Battery - Roadmap IKTS
RCC-40; 40 Ah
Natrium-Batterie
Keramische CERES / cerenergy®
große, vollkeramische Na-NiCl-Batterien (stationär)
QuantumScape
TRL 5 TRL 7 TRL 8 (VW)
Innovationsgrad / Disruption
Festelektrolyt
Keramischer
Keramische Festkörperbatterie
Lithium-Batterietechnik basierend auf vollständig anorganischen Komponenten
TRL 1 TRL3 TRL5 TRL7
Festelektrolyt
EMBATT2.0 Seeo
Polymerer
großflächige Bipolarbatterie basierend auf polymeren Elektrolyten in Lithium-Batterietechnik (Bosch)
TRL 2 TRL3 TRL5 TRL7
EMBATT1.0
großflächige Bipolarbatterie basierend auf konv. Lithium-Batterietechnik
Flüssiger Elektrolyt
TRL 5 TRL7
Konventionelle Lithium-Ionen-Technik
2017 2018 2019 2020 2021 2022 2023 2024 2025
© Fraunhofer
- Vertraulich -Fraunhofer
IKTS
Stationary Storage:
NiCl2 + 2Na ↔ Ni + 2NaCl, E0 = 2,58 V
cerenergy® – Na/NiCl2 battery system for stationary
energy storage
Basis: inexpensive local raw materials
material cost < 30 $ kWh
Good environmental compatibility main
components are common salt and nickel
Extremely safe, as no spontaneous combustion
can occur
Application:
Ideal for stationary storage in combination with
renewable energies (solar and wind energy)
cerenergy® – Na/NiCl2 battery
system for stationary energy
storage.
© Fraunhoferreduction of production cost by factor 10
Dry pressing
Flat substrates
Extrusion
∅ 20 bis 30 mm,
thickness 0,5 to 2 mm
Tubes ∅ 20 bis 60 mm,
wall. 1,5 mm, legth up
Isostatic pressing to 600 mm
cost-
reduction:
factor 10
Beakers ∅ 20 mm,
wall thickness. 1,5 mm,
length 150 mm
42
© Fraunhofer IKTSNa-Battery-Systems are less complex than Li-Systems
Na-Battery Li-Battery
+ 50°C
∆T = 250°C ∆T = -28°C
300 °C
- 30°C 22 °C
∆T = 330°C ∆T = 52°C
passive cooling (∆T > 0) active cooling + heating
Thermal self heating Lose of warrenty at +/- 2 Kelvin
No Air Conditioning Fire hazard at > 60 °C
Inherently safe / simple Massive power demand for air
BMS conditioning
© Fraunhofer 43Tertiary Elements: Brennstoffzelle
z.B. Solid Oxide Fuel Cell (SOFC) at IKTS
Material
MEA
Stack
System
3YSZ matrix
LSC catalyst
44 © Fraunhofer IKTSAdvantage of Fuel Cells:
Direct conversion of chemical energy into power
Hydrogen production reverse process:
by electrolysis Fuel Cell
45 © Fraunhofer IKTSStrategische Bedeutung der MCFC / Energiewende MCFC: > 250 kW
Fuel Cell Types
AFC PEM PAFC MCFC SOFC
80 °C 80 °C 200 °C 650 °C 850 °C
Oxidation-
gas O2 O2 H2O O2 H2O CO2 O2 O2 Luft exhaust
Cathode current
Electrolyte OH- CO3- - O--
load MCFC + SOFC
H+ H+ optimum
systems for
Anode CHP
H2 H2O H2 H2 H2 H2O H2 H2O exhaust
Fuelgas
CO CO2 CO CO2
SOFC: < 250 kW
Alkaline Polymer phosphoric Molten Solid
FC Electrolyte acid FC carbonate electrolyte
Membrane FC FC
FC
Multi Fuel capable.
Simple Reforming = conventional
Hydrocarbon fuels can be used no Pt !
46 © Fraunhofer IKTSIKTS Fuel Cell System Competence 1W 10 W 100 W 1 kW 10 kW 1 MW portable portable portable stationary stationary hydrogen Propane LPG NG Biogas + NG Biogas + NG Ethanol Tubular Ethanol SOFC SOFC MCFC PEFC SOFC SOFC Elektrolyse © Fraunhofer
1.0 www.ceragen.org - 48 -
Next Step with h2e system:
CCHP Fuel Cell with PV and battery components
total power grid independence !!
NG
PV-panel Conventional system for
(1-2 kWp) heating or/and absorption cooling
Heatinmg or Cooling
Heat
Heating / absorption cooling
PV-power
Hot water
Heat !
Power out Base power
2.0
Cold water
stationary-battery storage (NaNiCl)
Including DC/AC converter Water heat storage
www.ceragen.org - 49 -
- business confidential -Power generating stand by heating system
SOFC-based Range Extender
Benefits: 3.0
High efficiency for fuel to power conversion
=> ηel bis zu 40 %
Flexible Fuels
=> Diesel, gasoline, biogas, LPG, CNG, EtOH; H2
Dis-advantage
Limited power, poor dnamics
Added value:
Heat generation
=> „power generating stand by heating system“
Excess power can be used for feed in of power into home
=> „Reversed Plug-In Hybrid“
© Fraunhofer IKTS - 50 -SOEC (solid oxide electrolysis): Hydrogen generation and
value added producs from excess power, H2O and CO2
Combination of Co-
Electrolysis and
gasförmige
Fischer-Tropsch
Produkte Synthesis for efficient
production of high
cost chemicals (ηen bis
exhaust 55 %)
CO2-Separation Utilization of waste
heat is essential for
CO2
sufficiant efficiency
Synthesis reactor
Co-Electrolysis (e.g. Fischer
Gas-Liquid-
Separation
SOEC-Stacks already
Tropsch)
H2, CO available for Co-
Electrolyisis
Chemical New process and
H2O Products
reactor concepts
(e.g. waxes)
based on ceramic
materials are being
SOEC developed at IKTS
51
© FraunhoferCO2-Reduction
Stahlerzeugung
CO2-Nutzung CO2-Vermeidung
Carbon Capture and Utilization (CCU) Carbon Direct Avoidance (CDA)
Synthesegas über Co-Elektrolyse Substitution von Kohle
Kopplung von Elektrolyse und Synthese Nutzung von erneuerbarem Wasserstoff
Shutterstock, Oleksiy_Mark Shutterstock, M.Khebra
© FraunhoferIndustrielle CO2-Emissionen
Vergleich von CCU und CDA für die Stahlindustrie
Derzeit installierte Leistung: 56 GW***
8 Mio. t p.a. H2
60% + -
CCU
CH3OH
60%
Emissions-
Methanolsynthese
reduktion
5 Mio. t p.a.** 4,3 GW 1880 Windräder*
Schachtofen Energiebedarf
H2 pro vermiedener
+ - t CO2
4,3x
CDA
5 Mio. t p.a.** 95%
geringer!
Emissions-
Elektrolichtbogenofen reduktion 1,6 GW 700 Windräder*
* Annahmen: 4.000 Betriebsstunden p.a. mit einer Anlagenleistung von 5 MW ** Referenz: Rohstahlproduktion p.a. der Salzgitter AG
*** Die angegebene Leistung bezieht sich auf Deutschland im Jahr 2018 und unterliegt einem Zubau von rd. 3 GW p.a.
© Fraunhofer 53CO2-Emission Reduction
Electrolysis is core technology for CCU and CDA and Hydrogen economy !
Alkaline Electrolysis PEM-Electrolysis SOEC: High Temperature Electrolysis
©NEL ©AREVA
Industriell etabliert Demo/Anwendung Labor/Demo
Korrosive Medien Geringere Temperatur: ~800 °C
Lebensdauer
Geringe 3,0–4,2 kWh/Nm³ H2 + CO
Stromdichten 4,2–5,6 kWh/Nm³ H2
4,2–5,9 kWh/Nm³ H2
© FraunhoferKeramische Werkstoffe, Bauteile
haben ein vielseitiges Einsatzspektrum und sind aus der
modernen Industrie und Alltag nichtmehr wegzudenken
Werden in der Regel da eingesetzt wo andere Werkstoffe
versagen oder unikale Effekte realisiert werden müssen
können durch ausgefeilte Technologien /
mikrostrukturelles Design und entsprechende
konstruktive Auslegung so gestaltet werden, dass
katastrophales Versagen durch Sprödbruch
ausgeschlossen werden kann.
55 © Fraunhofer IKTSSie können auch lesen
