Constituent Materials Fibres

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1 Spring Semester L Manufacturing of Polymer Composites Constituent Materials Fibres 9 February 2017 Paolo Ermanni Manufacturing of Polymer Composites - Constitutent Materials

2 Thin fibers are stronger then bulk material A.A. Griffith ( ) The New Science of Strong Materials, J.E. Gordon Manufacturing of Polymer Composites - Constitutent Materials

Typical fibers for application un composites

isotropic properties Covalent bonding O-Atom

: Faserverbundbauweisen, Fasern und Matrices;

3 Typical fibers for application un composites Fiber Structure Features Carbon fibers 2D covalent bonding Graphene sheets High orientation degree Glass fibers Si-Atom 3D isotropic properties Covalent bonding O-Atom Aramid fibers 1D covalent bonding Linear molecules are oriented along fibre axis Flemming, M.; Ziegmann, G.; Roth S.: Faserverbundbauweisen, Fasern und Matrices; Springer-Verlag, Berlin Heidelberg 1995 Manufacturing of Polymer Composites - Constitutent Materials

4 Crystallite structure Transverse direction Fibre direction Strong covalent bonding Relatively weak Van der Waals forces between the sheets The achievable properties of the carbon fibers are strongly influenced by the precursor type, the processing route, and defects of the crystallite structure. McGuire, C.; Vollerin, B.: Thermal Management of Space Structures; SAMPE-European Chapter, 1990 Manufacturing of Polymer Composites - Constitutent Materials

5 Achievable fiber properties Young s modulus Strength [GPa] Theoretisch HT-Faser HM-Faser HT-Faser HM-Faser Theorertical Experimental Fitzer, E.: Neue Entwicklungen für Faserverbundwerkstoffe, Handbuch für neue Systeme; Hrsg. Demat Exposition Managing; Vulkan-Verlag, Essen 1992 Manufacturing of Polymer Composites - Constitutent Materials

6 Defects in the graphite structure Lattice vacancies Stacking faults Disclinations H. Heissler, Verstärkte Kunststoffe in der Luft- und Raumfahrt, Kohlhammer, Stuttgart Berlin, 1986 Manufacturing of Polymer Composites - Constitutent Materials

7 Effects of preferred orientation on the Young s modulus of carbon fibres H. Heissler, Verstärkte Kunststoffe in der Luft- und Raumfahrt, Kohlhammer, Stuttgart Berlin, 1986 Manufacturing of Polymer Composites - Constitutent Materials

8 Precursor materials Material C [%] H [%] N [%] O [%] S [%] Carbon yield [%] RAYON PAN MPP ,0 49-0, , Requirements: High carbon yield Spinnable in order to produce precurso fibres Good mechanical and thermal properties (high degradation temperature) Spengler, H.; van Galen, J.: Herstellung von Kohlenstoffasern aus Steinkohlenteerpech; BMFT-Verbundprojekt 03M1015; Verbundpartner: AKZO, Wuppertal; Rütgerswerke AG, Frankfurt; TU Karlsruhe; Universität Erlangen, 1990 Manufacturing of Polymer Composites - Constitutent Materials

9 Manufacturing process of PAN-based fibres Carbonise Graphitize PAN-HT PAN-HM PAN-HT PAN-HM PAN-HT: High Tenacity, PAN-HM: High Modulus 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 Manufacturing of Polymer Composites - Constitutent Materials

10 Oxidation/Stabilization Cyclization of the nitrile group Dehydrogenation of the C / C-chain by oxygen Carbonization 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 Manufacturing of Polymer Composites - Constitutent Materials

11 Selected properties of PAN-based carbon fibres Hochfest HT Intermediate IM Hochsteif HM Hochsteif /Hochfest HMS Dichte g/cm 3 Zugfestigkeit BZ GPa Zugmodul E Z GPa Druckfestigkeit Bd GPa Bruchdehnung BZ % Reisslänge BZ / km Dehnlänge E Z / km Faserdurchmesser d m Langzeiteinsatztemperatur T L C 1,74 3, ,50 1, ~ ,80 5, ,20 1, ~ ,83 2, ,50 0, ~ 6, ,85 3, ,80 0, ~ Sublimationspunkt T S C Flemming, M.; Ziegmann, G.; Roth S.: Faserverbundbauweisen, Fasern und Matrices; Springer-Verlag, Berlin Heidelberg 1995 Manufacturing of Polymer Composites - Constitutent Materials

Strength / Elasticity Modulus of PAN-based Carbon Fibers Toray Carbon Fiber Composite Materials Businesses, June 6, 2005, Masayoshi Kamiura, Managing

12 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 Manufacturing of Polymer Composites - Constitutent Materials

13 Manufacturing of pitch-based carbon fibres Carbonise Graphitize PAN-HT PAN-HM PAN-HT PAN-HM PAN-HT: High Tenacity, PAN-HM: High Modulus 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 Manufacturing of Polymer Composites - Constitutent Materials

14 Thermal expansion coefficent and thermal conductivity Quelle: McGuire, C.; Vollerin, B.: Thermal Management of Space Structures; SAMPE-European Chapter, 1990 Manufacturing of Polymer Composites - Constitutent Materials

15 Typical fibers for application un composites Fiber Structure Features Carbon fibers 2D covalent bonding Graphene sheets High orientation degree Glass fibers Si-Atom 3D isotropic properties Covalent bonding O-Atom Aramid fibers 1D covalent bonding Linear molecules are oriented along fibre axis Flemming, M.; Ziegmann, G.; Roth S.: Faserverbundbauweisen, Fasern und Matrices; Springer-Verlag, Berlin Heidelberg 1995 Manufacturing of Polymer Composites - Constitutent Materials

Relationship between temperature and specific volume Glass is a ceramic material with a specific feature: Below a transformation region (Glass transition temperature) the toughness is so high

16 Relationship between temperature and specific volume 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 further plastic state, and finally it converts into a solid brittle state. Silica is atypical glass former Si-Atom O-Atom The point at which the curve changes slope is called glass transition temperature Flinn R., Trojan P., Engineering Materials and their Applications, Houghton Mifflin Company, Boston, Manufacturing of Polymer Composites - Constitutent Materials

1.4, Glasfasern; Springer Verlag, 1961 Manufacturing of Polymer

17 Manufacturing of glass fibres Nozzle-drawing process for production of glass fibers Source: Hagen, H. u.a.: Glasfaserverstärkte Kunststoffe, Kap. 1.4, Glasfasern; Springer Verlag, 1961 Manufacturing of Polymer Composites - Constitutent Materials

18 Selected properties of glass fibres E R/S M C D Q Zugfestigkeit GPa E-Modul GPa Bruchdehnung % spez. Zugfestigkeit GPa x cm 3 /g spez. E-Modul GPa x cm 3 /g 3,5 73 ~ 4,5 1,38 28,8 4,7 88 5,0 1,8 34 7,0 125 ~ 5,5 2,8 50,3 3,1 71 3,5 1,3 29 Faserdurchmesser m Dichte g/cm , , ,45 therm. Ausdehnungskoeffizient 10-6 /K ,2 Schmelzpunkt C E: elektrisch C: chemisch resistent R/S: hochfest D: dielektrisch M: steif Q: Quarz Quelle:Kleinholz, R.: Neue Erkentnisse bei Textilglasfasern zum Verstärken von Kunststoffen; 22. Internationale Chemiefasertagung, Dornbirn 1983 Manufacturing of Polymer Composites - Constitutent Materials

19 Typical fibers for application un composites Fiber Structure Features Carbon fibers 2D covalent bonding Graphene sheets High orientation degree Glass fibers Si-Atom 3D isotropic properties Covalent bonding O-Atom Aramid fibers 1D covalent bonding Linear molecules are oriented along fibre axis Flemming, M.; Ziegmann, G.; Roth S.: Faserverbundbauweisen, Fasern und Matrices; Springer-Verlag, Berlin Heidelberg 1995 Manufacturing of Polymer Composites - Constitutent Materials

General consideration Applications: http://www.dyneema.

20 General consideration Applications: Manufacturing of Polymer Composites - Constitutent Materials

Spherulites: spherical semi-crystallites of folded chains Baer, E.

21 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 Manufacturing of Polymer Composites - Constitutent Materials

22 Orientation of the chains in the semi-crystalline polymer Bridging molecule Manufacturing of Polymer Composites - Constitutent Materials

23 Rigid rod polymers PPTA (poly-para-phenylene terephthalamide), Source: 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 Source: Blumberg, H.: Stand und Entwicklungstendenzen für Hochleistungs- Polymer- und Kohlenstoffasern; 28. Internationale Chemiefasertagung, Dornbirn September 1989 Manufacturing of Polymer Composites - Constitutent Materials

24 Manufacturing of aramide fibers Quelle: Ehrenstein, G.W.: Faserverbund-Kunststoffe, Werkstoff-Verarbeitung-Eigenschaften; Carl Hanser Verlag, München 1992 Manufacturing of Polymer Composites - Constitutent Materials

Structure and properties of aramide fibres Quelle: Morgan, R.J.

Reinforcements, pp. 5-22, Edited by Lee, S.M.

Kennwert Einheit 29 49 149 Dichte g/cm 3 Zugmodul GPa

Faserdurchmesser µm 1.44 83 4,0 3.62 1.44 124 2,9 3.62 1.47 186 2,0 3.

25 Structure and properties of aramide fibres 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 Mechanical properties Kennwert Einheit Dichte g/cm 3 Zugmodul GPa Zugbruchdehnung % Zugfestigkeit GPa Druckfestigkeit GPa Faserdurchmesser µm , , , im UD-Verbund ca. 30% der Zugfestigkeit Manufacturing of Polymer Composites - Constitutent Materials

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