Jun 15, 2015 - Dr. Michael Heine. University of Augsburg / Chair Materials Engineering. Institute for Materials Resource Management (MRM). Chair of. Physics.
Overview of CF Processing Prof. Dr. Michael Heine University of Augsburg / Chair Materials Engineering Institute for Materials Resource Management (MRM)
MRM Institute
Chair of Physics
Abstract •
Carbon fibers are one of the strongest known materials today. In the early 1960s they were highlighted as a "Rider of a New Industrial Revolution" and as an initiator of a new “Carbon Age”. In Europe, the SIGRI Elektrographit GmbH, Meitingen / Germany started in the late 60s one of the first industrial pilot plant in the world. Since that, the most important established precursor materials is polyacrylonitrile. The chemical conversion of the precursor into an unmeltable ladder structure with following elimination of nitrogen atoms and the formation of graphitic carbon layers characterizes the production process. These conversion reactions are very complex and up to now not fully understood. Some of them are extremely exothermic what means a challenge for the process control. The actual technology for CF processing, concerning the chemical and physical processes as well as the parameters defines the key elements forming high-strength carbon-carbon bonds within the fiber structure. It is obvious that alternative precursor material will have similar complexity when creating carbon fibers.
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Short CV 1982 - 1988 University (TU) of Karlsruhe / Institute for Chemical Technology (ICT) / •
Prof. Erich Fitzer Scientific Assistent Thesis „Optimization of the reaction conditions of thermoplastic polymer fibers like polyacrylonitrile for carbon fiber production”
1988 - 2014 SGL CARBON GmbH / SGL GROUP – The Carbon Company • • • • • • • •
R&D Manager Fibers Technology & Production Manager Fibers Head of Technology & Prototype Production - Carbon Composites / Fuel Cell Head of Technology & Prototype Production - Carbon & Ceramic Composites Head of Technology Ceramic Composites Director Innovation Management & Deputy Director R&D Director Public Funding SGL Group Director Scientific Cooperation / Technology & Innovation / NBD
2013 - Today University of Augsburg / Institute for Materials Resource Management • 3
Chair Materials Engineering Overview of CF Processing
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Carbon Composites in the European Context
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Leading Edge Cluster initiated by the Competence Network CFK Valley Stade
Luftfahrt
Prozesse & Composites Aachen
Dresden
Prozesse & Composites
Kaiserslautern
Thermoplaste Karlsruhe Augsburg Stuttgart
München
Budget 80 Mio. € / 2012 - 2016 5
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Interdisciplinary Approach University
Institutes for Prozess Technology MRM Institute Chair of Physics
Interdisciplinary Institute Interdisziplinäres Institut Materials Materials Resource Research Management Management
Basic Research
DLR ZLP und Fraunhofer FIL Applied Research
Technology Center
End-User
Innovation Park Augsburg 6
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Process Chain Carbon Composites
Fiber
Textile Textile
Polymer
Composite
Polymer
Precursor
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Stabilized Fiber
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Carbon Fiber
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Re-Use
CARBON is Future FILM: Carbon is Future – Carbon is SGL Group http://www.sglgroup.com/cms/international/company/corporateprofile/corporate-video/index.html?__locale=de
FILM
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Process Chain Carbon Composites The Material and Process Competence of SGL GROUP includes the entire Process Chain of Carbon Composites
FILM
http://www.sglgroup.com/cms/international/innovation/from-fibers-to-components.html?__locale=de
Fiber
Textile Textile
Polymer
CFRP
CFRC
Polymer
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CSiC
Process Chain Carbon Fiber Precursor
Racking
Stabilised Fiber
Stabilisation
Carbon Fiber
Carbonisation Surface Treatment
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Winding Deposition
Carbon Fibers Pre-Conditions
Definition: Carbon Fibers are commercial produced fibers based on carbon containing precursor materials which are converted into a special carbon structure with high tensile strength.
The conversion of the precusor material must be cost-effective with stable process conditions
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Precursor Carbon Yield
In principle all materials containing carbon are suitable to form pure carbon structures
at T > 500 °C in Nitrogen-Atmosphere Carbon Yield > 20 w.% „Prezel“ (German Pastry)
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Carbon Chemical Bonding and Structure (1)
Based on his special electron configuration carbon has outstanding physical properties and the ability to form complex structure modifications and molecules.
c
120°
b a
B A
c = 0.67 nm
A 120°
120°
sp² hybridization a = 0.14 nm
Graphite: hexagonal (ABAB...)
Graphit
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Carbon Chemical Bonding and Structure (2)
Based on his special electron configuration carbon has outstanding physical properties and the ability to form complex structure modifications and molecules.
109.3°
Diamond: cubic
sp³ hybridization
Diamond (honed) 14
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C-Fiber „contra“ Metals Theoretical Strength of the C-C-Bonding
Theorie: 100.000 MPa Praxis:
7.000 MPa Torayca T 1000 (1986)
Raw Iron: 200 MPa Cupper: 220 MPa Aluminium: 450 MPa (2014-T6) Brass: 550 MPa Steel high strength: 760 MPa (ASTM A 514) Titanium alloy: 900 MPa (6% Al, 4% V) Wolfram: 1.510 MPa Steel Fibers: 1.900 MPa 15
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Failure Behaviour Carbon Fiber / Metal Tensile Strength
Maximal Range of Use
Carbon Fiber
Tensile Strength
Metal Quelle: Wikipedia
Elongation at break [%]
Carbon Fibers in contrary to Metals don‘t show any plastic flow when reaching the maximal range of use 16
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History of Carbon Material (1)
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Traditional Carbon Material
New Carbon Material
Year 1800 >>
Year 1960 >>
Graphite Elektrodes
Graphite Crucible
for Fe-, Al- & SiProduction
for Semiconductor- and Solar PanelProduction
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Graphite Components
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for Chemical Apparates Engineering
History of Carbon Material (2) New Carbon Material
New Carbon Modifications
1960 >>
1985 >>
Human Hair
Carbon Fiber
Battery Felt for Batteries GDL for Fuel Cells
1985
1991
2004
Fullerenes
Nanotubes
Graphene
Kroto, Curl & Smalley
S. Iijima
Geim, Novoselov
CF-Thermoplast Tape
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The first C-Fiber
Thomas Alva Edison - Erfinder der Kohlenstofffaden-Glühbirne (Bild: AP Archiv) Photo: Ulf Seifert
Edisons Glühlampe, Abb. aus Meyers Konversationslexikon 1888
Production of glow filaments based on bamboo fibers (1881) 19
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C-Fibers with a principal short history 70.000 t/a 50.000 t/a Gebr. Siemens & Co (Gesco) Start of Carbon Material Production
o 30.000 t/a 10.000 t/a
Polyacrylnitril (PAN)
1880
1900
1920
1940
1960
Shindo C-Fiber based on PAN Edison Light Bulb
20
1980
SGL 1st Carbon FiberPplant
Rolls-Royce CFRP for Aircraft Engines Overview of CF Processing
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2020
2040
JV SGL / BMW Carbon Fiber Plant Moses Lake USA SGL Carbon Fiber Plant MoO Schottland
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Precursor Types Market Share
CarbonYield (ca.)
Material Characteristics
Market Share
Polyacrylonitrile
50 %
Middle / High Modulus High / Very High Strength
95 %
Mesophase Pitch
80 %
Very High Modulus Low / Middle Strength
50 w.% Heine, M., Diplomarbeit TU Karlsruhe 1982
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Carbon Yield = f (Temperature Profile at Stabilisation) 1,415 g/cm3
einstufig, isotherm einstufig, nichtisotherm
1,44 g/cm3
zweistufig, isotherm
1,40 g/cm3
A high carbon yield depends on the temperature profile at the stabilisation step
Heine, M., Dissertation TU Karlsruhe 1988
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CFiber-Density = f (Stab. time / -conditions)
zweistufig, isotherm einstufig, nichtisotherm
einstufig, isotherm
With best stabilisation conditions the density of the resulting carbon fibers are in the range of 1,75 to 1,78 g/cm3
Heine, M., Dissertation TU Karlsruhe 1988
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Reaction Shrinkage = f (Stab. time / -conditions)
zweistufig, isotherm
eineinstufig, isotherm stufig, nicht- isotherm
Shrinkage in a range of 10 - 13 % correlates with optimal stabilisation conditions
Heine, M., Dissertation TU Karlsruhe 1988
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CFiber-Strength = f (Stab. time / -conditions)
1,415
1,40
1,45
1,415 1,395
1,405
[g/cm3]
zweistufig, isotherm
1,425
1,48
1,398
eineinstufig, isotherm stufig, nicht- isotherm 1,375
1,43 1,445
1,415
Heine, M., Dissertation TU Karlsruhe 1988
Maximal Tensile Strength correlates with different target densities reached by different temperature profiles at stabilisation 64
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CFiber-Strength = f (Stab. conditins / Oxygen Content)
The stabilisation process influences the the oxygen uptake
There is a correlation between an optimal oygen content after stabilisation and the maximal tensile strength Heine, M., Dissertation TU Karlsruhe 1988
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Tensile Strength/Youngs Moduls = f (Stab. conditins / Carbonisation Temperature)
Quelle: Fitzer, E., Frohs, Heine, M., Optimization of stabilization and carbonization of PAN fibres and structural characterisation of the resulting carbon fibres. In: Carbon 24 (1986), Nr. 4, S. 387-395
Tensile Strength and Youngs Modulus are defined by the carbonisation temperature 66
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Graphit(ic) Structure = f (Material / Carb. temperatur)
Pitch PAN Uni Augsburg, 2003
ideales Graphitgitter
The formation of graphitic layers and the reduction of the layer distance is an essential phenomenon of the carbonisation process
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Structural development of carbon in the carbon fiber (Source: Marsh, H: A tribute to Philip L. Walker. In: Carbon 29 (1991), No. 6, pp. 703–704)
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Graphitic Layers Degree of Orientation
The perfect fomation of the graphitic layers is one of the essential preconditons for a high Youngs Modulus of the Carbon Fiber 68
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Youngs Modulus = f (Orientation Degree of the graphitic layers)
The Youngs Modulus increases with the orientation degree of the graphitic layers The surface of the carbon structure is determining the Fiber-Matrix-Interaction 69
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Prozess Chain schematic
Quelle: Sahm, Eschwege
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Surface Treatment Anodic Oxidation & Finishing
Electrochemical formation of polar surface groups as coupling agent between the fiber surface and the finish/matrix
untreated
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Fiber
Surface Activation
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Deposition of film former and adhesion promoter between matrix and fiber
Finishing
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Fiber
Surface treated
Fiber / Matrix an old topic https://www.dondereciclo.org.ar/blog/biocontruccion-con-barro-unaalternativa-sustentable/
maetzler.blogspot.com
African Loam Construction
Loam Brick
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Composite „Nothing has endless life“
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Composites are everywhere
„No real light weight construction“
es.wikipedia.org http://www.arch-forum.ch/dictionary/details/es/133
Reinforced Concrete 74
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Interaction Fiber / Matrix Basic conditions
Finish
Carbon-Fiber
CFRP must have a strong interaction between the fiber surface and the matrix to realise the fiber strength and modulus within the structural component Matrix
Polar Surface Groups
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The interaction defines the failure mechanism under load The fiber / matrix interaction has to be controlled by suitable actions
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Fiber / Matrix Involved Components and their Functions
• Matrix – Transfer of external load into the carbon fiber – Protection of the fiber – Mechanical fixation of the fiber position within the composite
Carbon-Fiber
Finish
• Finish Matrix
– Good wettability of the fiber surface in contact with the matrix polymer – Good physical and und chemical connection between the poylmerised matrix and the fiber surface
• Fiber Surface Polar Surface Groups
– Interaction to the finish and to the matrix – Allocation of polar surface groups as connecting points
• Carbon Fiber – Uptake and transfer of external loads – Force adapted positioning within the composite 76
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Anodic Oxidation
N
Ib
COOH
Ia II CHO
IV O
III OH N
·
C
·
Jäger, H. Dissertation TU Karlsruhe 1986
The interlaminar shear strength (ILSS) is an indicator for interface adhesion between fiber and matrix Polar und reactive groups on the fiber surface define the adhesion
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C-Fiber Producer USA / Europe / Asia
Grimsby, UK
Budapest, HU Greenville, SC
Mishima, JP
Kelheim + Meitingen, GER Lanzhou, CN
Decatur, AL Guadalajara, MEX
Otake, JP Mitsubishi
Taiwan, CN Ehime, JP
Formosa Plastics
Source: SGL Carbon 2013
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Development of Costs C-Faser (since 1960)
140.000 t/a 100.000 t/a 60.000 t/a PAN
1880
1900
1920
1940
1960
20.000 t/a
1980
2000
2020
2040
500 € / kg
Edison Light Bulb
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10 € / kg
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C-Fiber Key Costs 100
Cost Share
[%]
PAN Precursor
45
Energy
20
Manpower
10
40
Maintenance
8
20
Chemical Processes
8
Others
9
Status: 2014
[€/kg]
80
Price
60
High-End
0
Standard Industry
Aerospace
1k
3k
6k
12k
50k
320k
Number of Filaments [single cable] 80
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CF-Types Nomenclature 7000
Standardisierung der Begriffe durch:
StrengthStrength [MPa] Tensile [MPa]
IntermediateModulus
International Union of Pure and Applied Chemistry (IUPAC), zu deutsch „Internationale Union für reine und angewandte Chemie“
6000
HighModulus 5000
UltraHighModulus
(Gründung: 1919) http://www.iupac.org/
4000
HighTensilestrength 3000 100
300
500
700
900
Stiffness [GPa]
Young‘s Modul [GPa]
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CF-Types
Tensile Strength [MPa]
Precursor related
IM Polyacrylnitril (PAN) based
HT
HM
Pitch based
UHM Young‘s Modulus [GPa] 82
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CF-Types
Tensile Strength MPa]
Market related
IM
www.aerospacetechnology.com
Aviation Qualities Airbushelicopters.com
HT
HM
Space Flight Qualities en.wikipedia.org
plainswindeis.anl.gov
Industry Qualities
UHM
bmw.com
Young‘s Modulus [GPa]
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Price Development Large Scale Markets C-Fiber
Large Scale Markets will dominate the future of the carbon fiber
500 Space flight
Price €/kg
Military
Sport
en.wikipedia.org
Industry birminghampost.co.uk
Racing
Aviation
Energy Automotive
ferrari.com Airbus.com wordlesstech.com
www.daimler.com/
Civil Engineering
10 1970
84
1980
1990
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2000
2010
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2020
Market Penetration = f (Time to Market)
Market Penetrationg [log t/Jahr]
10.000.000
4-5 Mio t/a 1.000.000 100.000 Carbon Fiber
10.000 1.000
40 kt/a
Al2O3 Fiber
100 SiC Fiber
Marktet Penetration is following a logarithmic principles
10 1
85
Glass Fiber
0
40 20 Time to Market [Years] Overview of CF Processing
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Carbon Fibers Coparison of Market Relevance Capacity of classical materials [tons/year] in comparison to carbon fibers (Status 2010)
Global Demand of Carbon Fibers [tons/year] for 2008–2020 (*estimated) Composite Market Report 2014 CCeV / AVK [1] [2]
Lucintel LLC, Growth Opportunities in Global Carbon Fibre Market: 2014-2019, Irving, USA, 2014. Acmite Market Intelligence e.K., Market Report: Global Carbon Fiber Composite Market, Ratingen, 2014.
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Costs CFRP Process Chain Material Production
Stacking
Cutting
RTM
Machining
Polymer
Semifinished Products Fiber Fabrics NCF
25%
50%
20%
5%
Main cost driver is preforming and missing of automation 87
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CFRP Costs Prediction
CFRP Costs 100 %
CFRP Process
Key Aspects for Cost Reduction
Cost Prediction [ €/kg] 30
20 75 %
Polymer
5%
Carbon Fiber
20 %
Process Optimized Polymers
New Precursor & Processes
10
1
2
Steel
3
2005
4
5
6
20121
Quelle: Benteler SGL
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7
8
Aluminium
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9
10
11
CFRP
2020
Any Questions ?
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