constituent materials fibres - eth z · 2017-03-09 · eth zurich, laboratory ofcomposite materials...

||ETH Zurich, Laboratory of Composite Materials and Adaptive Structures

9 February 2017Paolo Ermanni

Constituent MaterialsFibres

Spring Semester 2017

151-0548-00L Manufacturing of Polymer Composites

09.03.2017Manufacturing of Polymer Composites - Constitutent Materials 1


„The New Science of Strong Materials“, J.E. Gordon

Thin fibers are stronger then bulk material

A.A. Griffith (1893-1963)



Typical fibers for application un composites

2D covalent bonding Graphene sheets High orientation degree

Fiber Structure Features

1D covalent bonding Linear molecules are oriented

along fibre axis

Carbon fibers

Glass fibers

Aramid fibers

Si-Atom

O-Atom

3D isotropic properties Covalent bonding

Flemming, M.; Ziegmann, G.; Roth S.: Faserverbundbauweisen, Fasern und Matrices; Springer-Verlag, Berlin Heidelberg 1995


||ETH Zurich, Laboratory of Composite Materials and Adaptive StructuresMcGuire, C.; Vollerin, B.: Thermal Management of Space Structures; SAMPE-European Chapter, 1990

Crystallite structure

Strong covalent bonding Relatively weak Van der Waals forces between the sheets

Fibre direction

Tran

sver

se d

irect

ion

The achievable properties of the carbon fibers are strongly influenced by the precursor type, the processing route, and defects of the crystallite structure.



Achievable fiber properties

Young‘s modulus Strength [GPa]

5 3

25

70

HT-Faser HM-Faser

1050

250

700

Theoretisch HT-Faser HM-Faser

Fitzer, E.: Neue Entwicklungen für Faserverbundwerkstoffe, Handbuch für neue Systeme; Hrsg. Demat Exposition Managing; Vulkan-Verlag, Essen 1992

Theorertical Experimental



Defects in the graphite structure

H. Heissler, Verstärkte Kunststoffe in der Luft- und Raumfahrt, Kohlhammer, Stuttgart Berlin, 1986

Lattice vacancies Stacking faults Disclinations



Effects of preferred orientation on the Young‘smodulus of carbon fibres

H. Heissler, Verstärkte Kunststoffe in der Luft- und Raumfahrt, Kohlhammer, Stuttgart Berlin, 198609.03.2017Manufacturing of Polymer Composites - Constitutent Materials 7


Precursor materials

Requirements:

– High carbon yield– Spinnable in order to produce precurso fibres– Good mechanical and thermal properties (high degradation

temperature)

Material

RAYONPANMPP

C[%]

456894

H[%]

664

N[%]

-241,0

O[%]

49-

0,6

S[%]

--

0,4

Carbon yield[%]

204585

Spengler, H.; van Galen, J.: Herstellung von Kohlenstoffasern aus Steinkohlenteerpech; BMFT-Verbundprojekt 03M1015; Verbundpartner: AKZO, Wuppertal; Rütgerswerke AG, Frankfurt; TU Karlsruhe; Universität Erlangen, 1990



R.J. Diefendorf; “Carbon / Graphite Fibers“, in Engineered Materials Handbook, Volume 1, Composites; ASM International Metals Park, OH, USA, 49-53, 1987 Fitzer, E; Weiss, R.: Oberflächenbehandlung von Kohlenstoffasern, Verarbeiten und Anwenden kohlenstoffaserverstärkter Kunststoffe; VDI-Verlag, Düsseldorf 1989

PAN-HT: High Tenacity, PAN-HM: High Modulus

Carbonise Graphitize

PAN-HT PAN-HM PAN-HT PAN-HM

Manufacturing process of PAN-based fibres



Oxidation/Stabilization

Carbonization


• Cyclization of the nitrile group • Dehydrogenation of the C / C-chain by

oxygen

The carbonization is carried out at rising temperatures of up to 1500 ºC, leading to pure carbon rings. This step takes place in a nitrogen atmosphere.

• Inhert environment• Slight tension -C-rings are oriented along the fibre axis• Fibre diameter reduces due to the removal of non-C-elements• Crosslink in lateral direction by dehydration and de-Nitorgenation



Selected properties of PAN-based carbon fibres

1,743,602402,501,50206

13800~ 75003600

HochfestHT

IntermediateIM

HochsteifHM

Hochsteif /Hochfest

HMS

1,805,602904,201,93311

16100~ 55003600

1,832,304001,500,57125

21850~ 6,55003600

1,853,605501,800,65194

29730~ 55003600

Dichte g/cm3

Zugfestigkeit BZ GPaZugmodul EZ GPaDruckfestigkeit Bd GPaBruchdehnung BZ %Reisslänge BZ/ kmDehnlänge EZ / kmFaserdurchmesser d mLangzeiteinsatztemperatur TL °CSublimationspunkt TS °C



Strength / Elasticity Modulus of PAN-based Carbon Fibers

Toray Carbon Fiber Composite Materials Businesses, June 6, 2005, Masayoshi Kamiura, Managing Director of the Board, General Manager, Torayca & Advanced Composites Division



Carbonise Graphitize

PAN-HT PAN-HMPAN-HT PAN-HM

Manufacturing of pitch-based carbon fibres

R.J. Diefendorf; “Carbon / Graphite Fibers“, in Engineered Materials Handbook, Volume 1, Composites; ASM International Metals Park, OH, USA, 49-53, 1987 Fitzer, E; Weiss, R.: Oberflächenbehandlung von Kohlenstoffasern, Verarbeiten und Anwenden kohlenstoffaserverstärkter Kunststoffe; VDI-Verlag, Düsseldorf 1989

PAN-HT: High Tenacity, PAN-HM: High Modulus



Quelle: McGuire, C.; Vollerin, B.: Thermal Management of Space Structures; SAMPE-European Chapter, 1990

Thermal expansion coefficent and thermal conductivity







along fibre axis

Carbon fibers

Glass fibers

Aramid fibers

Si-Atom

O-Atom





Relationship between temperature and specificvolume

The point at which the curve changes slope iscalled glass transition temperature

Flinn R., Trojan P., Engineering Materials and their Applications, Houghton Mifflin Company, Boston, 1990.

Si-Atom

O-Atom


Glass is a ceramic material with a specific feature: Below a transformation region (Glass transition temperature) the toughness is

so high (super-cooled liquid), that the body will first enter a furtherplastic state, and finally it converts into a solid brittle state.

•Silica is atypical glass former


Source: Hagen, H. u.a.: Glasfaserverstärkte Kunststoffe, Kap. 1.4, Glasfasern; Springer Verlag, 1961

Manufacturing of glass fibres


Nozzle-drawing process for production of glass fibers


Quelle:Kleinholz, R.: Neue Erkentnisse bei Textilglasfasern zum Verstärken von Kunststoffen; 22. Internationale Chemiefasertagung, Dornbirn 1983

3,573

~ 4,51,3828,8

3 - 132,555 - 6840

E R/S M C D Q

4,7885,01,83410

2,494

1000

7,0125

~ 5,52,850,310

3,1713,51,329

2,457,2

E: elektrisch C: chemisch resistentR/S: hochfest D: dielektrischM: steif Q: Quarz

Zugfestigkeit GPaE-Modul GPaBruchdehnung %spez. Zugfestigkeit GPa x cm3/gspez. E-Modul GPa x cm3/gFaserdurchmesser mDichte g/cm3

therm. Ausdehnungskoeffizient 10-6/KSchmelzpunkt °C

Selected properties of glass fibres







along fibre axis

Carbon fibers

Glass fibers

Aramid fibers

Si-Atom

O-Atom





General consideration


Applications: http://www.dyneema.com/emea/


Crystallinity in thermoplastic polymers

Semi-crystalline polymers form crystallites of folded chains entangled with bridging molecules in the amorphous phase between the crystallites.


Spherulites: spherical semi-crystallites of folded chains

Baer, E., Hochentwickelte Polymere; Spektrum der wissenschaft, Heidelberg, 1996


Orientation of the chains in the semi-crystalline polymer


Bridging molecule


Source: Blumberg, H.: Stand und Entwicklungstendenzen für Hochleistungs- Polymer- und Kohlenstoffasern; 28. Internationale Chemiefasertagung, Dornbirn September 1989

„Rigid rod“ polymers

Source: Morgan, R.J.; Allred, E.A.: Aramid Fiber Composites, Handbook ofComposites Reinforcements, pp. 5 - 22, Edited by Lee, S.M.; VCH-Verlagsgesellschaft, Weinheim 1993


PPTA (poly-para-phenylene terephthalamide),


Quelle: Ehrenstein, G.W.: Faserverbund-Kunststoffe, Werkstoff-Verarbeitung-Eigenschaften; Carl Hanser Verlag, München 1992

Manufacturing of aramide fibers



Quelle: Morgan, R.J.; Allred, E.A.: Aramid Fiber Composites, Handbook of Composites Reinforcements, pp. 5 - 22, Edited by Lee, S.M.; VCH-Verlagsgesellschaft, Weinheim 1993

Structure and properties of aramide fibres

Mechanical propertiesKennwert Einheit

1.44834,03.62...12

1.441242,93.62...12

1.471862,0

3.44...12

29 49 149

Dichte g/cm3

Zugmodul GPaZugbruchdehnung %Zugfestigkeit GPaDruckfestigkeit GPaFaserdurchmesser µm

im UD-Verbund ca. 30% der Zugfestigkeit


constituent materials fibres - eth z · 2017-03-09 · eth zurich, laboratory ofcomposite materials...

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