GRUPO GRUPO ANT O ANT LIN LIN CARBON CARBON NANOFIBER S NANOFIBER (GANF) 1

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Denis Parks
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1 GRUPO ANTOLIN CARBON NANOFIBERS (GANF) 1

2 Floating Catalyst Method Partículas Catalyst de catalizador solution en disolución (Fe, Co, Ni ( Fe, compound) Co, Ni, ) VIII group C x x H y + S compuesto compound de + S Salida Gas de H + 2 H 2 gases exit Reducción y dispersión del metal Temperature: ºC Inicio del crecimiento del filamento Crecimiento longitudinal y posible engrosamiento pirolítico CNF Salida Gas de exit gases Modificado de M.Endo; Americal Chemical Society, CHEMTECH, september, pp , (1988) The «floating» catalyst is introduced continuosly in the reaction chamber. Hidrocarbons decompose over its surface. The CNFs grow and swell. 2

3 State of art of GANF s technology n Grupo Antolin is manufacturing Carbon Nanofibres continuously at industrial i scale by the floating catalyst t technique. n The product manufacturing method developed and implemented is the cheapest one reported because of the low cost raw materials used. n The quality of the currently fabricated Carbon Nanofibres is excellent. 3

4 State of art of GANF s technology: EP A1: FURNACE FOR THE MANUFACTURE OF CARBON FIBRES, PROCEDURE FOR OBTAINING USING SAID FURNACE AND THE FIBRE THUS OBTAINED EP A1: GAS REUSING SYSTEM FOR CARBON FIBRE MANUFACTURING PROCESSES 4

5 State of art of GANF s technology: EP A1: CARBON NANOFIBERS AND PROCEDURE FOR OBTAINING SAID NANOFIBERS EP : PROCEDURE FOR THE ELIMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND OTHER VOLATILE AND SEMI VOLATILE COMPOUNDS IN CARBON NANOFIBRES 5

6 Furnaces developed by Grupo Antolin for the production and surface treating ti of GANF: 6

7 Grupo Antolin Carbon Nanofibres (GANF): Morphology and TEM diameter distribution ib ti 7

8 GANF technical data sheet 8

9 9

10 GANF graphitic structure Graphitic structure: Helix spiral stacked cup No presence of pyrolytic amorphous carbon Highly graphitic i material il 10

11 GANF graphitic structure Continuous ribbon rolled along the fiber axis. 11

12 GANF based available products Powder: HDPE bags with 250 g. of GANF Thermoplastic Materbatches. Stable suspensions in solvents, paints or dispersions in resins Conductive ceramics Nanopreg 12

13 GANF carbon nanofibres properties GANF carbon nanofibres contribute to improve the materials with the following properties: Electrical properties Electrochemical properties Thermal properties CARBON NANOFIBRES GANF Tribological properties Mechanical properties 13

14 GANF carbon nanofibres applications Conductive Adhesives Microelectronics Sensors Enhanced Thermal Management EMI Shielding Rocket ablative nanocomposite Conductive Coatings and Paints Lightweight i antennas and Ground planes Microwaves absorption Aerospace and Aeronautic Automotive Fuel system Paintable parts Exterior panels Embeded electronics Brake systems Engine parts Bipolar plates FC Electrode catalyst support PEMFC Supercapacitors Lithium ion batteries Energy CARBON NANOFIBERS GANF Electronic Materials for ESD Components of hard disc EMI shielding Semiconductor Conductive Adhesives Microelectronics Sensors Computers Functional textiles Textil Chemistry Catalyst support 14

15 Automotive applications 15

16 Objetivos del nuevo proyecto GANF carbon nanofibres in exterior polymer matrix applications: electrostatic t ti painting Painting drops go out the nozzle with a positive charge proportional to the voltage Body car is connected to the ground and attracts the charges The matrix polymeric composite can be painted together with therestoftheautobodyandtreatedinthesameprocessthat the metallic materials Mirror housing Advantages Very uniform surface and thin coating Perfect finish Little paint is necessary Reduction of costs Low emissions Fender Bumper 16

17 Fuel system: ESD applications Compounds used to manufacture fuel lines consisting of both monowall tubing and multi layer tubing. O rings Fuel tanks Fuel pipes HDPE Nylon 11 and 12 Fuel pumps Fluoropolymer compound Nylon 11 and 12 17

18 Adhesives with thermal conductivity n Addition of GANF carbon nanofibers to the adhesive improves its thermal conductivity considerably n Substitution of the metallic content in the commercial adhesives by GANF carbon nanofibers allows a reduction of weight n The Coefficient of Thermal Expansion (CTE) of carbon nanofibers is lower than that of metals, it improves dimensional stability of conductive adhesives Thermal conductivity: 1950 W/mK Thermally conductive adhesive with carbon nanofibers for dissipation of heat in electronic circuits 18

19 High performance brakes GANF Carbon Nanofibres can be used in discs and pads for high performance brakes, since they present excellent tribological properties: BRAKES CARBON CARBON: C C composites with carbon fibres in a carbon matrix additionally reinforced with carbon nanofibres BRAKES CERAMICS CARBON: CARBON: high tech ceramic matrix composites society.org/ with GANF carbon nanofibres content 19

20 Multifunctional composites: mechanical properties improvement GANF carbon nanofibers increase easily the rigidity of the resins The optimization of surface characteristics of carbon nanofibers allows to obtain a good adhesion to the matrix improving the mechanical resistance of the material Improvements have been obtained in tribological properties, fatigue, ILSS and ductility properties The properties are also achieved in the Z direction of the composite material, perpendicular to the laminate of the continuous carbon fibers 20

21 High crystalline single-layer l graphene nanoplatelets from GANF carbon nanofibers 21

22 What is graphene? Structure of graphite Graphene one layer 22

23 What is graphene? Peierls (1935), Landau (1937), Mermin (1968): 2D crystals are not thermodynamic stable and cannot exit. They always form 3D structures. But Novoselov oselo et al. Science (2004) 23

24 Singular properties p Electronical properties Zero-gap semiconductor High electronic transport (~ cm 2 V -1 s -1 ) Combination o of: Electrical ca conductivity, ty, transparency and flexibility Mechanical and thermal properties High thermal conductivity it evenat room temperaturet (~5000 Wm -1 K -1 ) (Nano Lett. 8, 902 (2008)) High mechanical strength(~130gpa) & modulus (~1TPa) (Science 321, 385 (2008)) 24

25 GRAnPH applications Electronic Energetic Structural Ultra-High speed Transistors Touch panels Supercapacitors Solar cells Batteries Polymer nanocomposites Aligned over substrate 25

(2009) Thermal decomposition of SiC: van Bommel et al. (1975), Forbeaux et al.

26 Graphene synthesis Graphene Epitaxial growth CVD on metal substrates (Ni, Pt, TiC, Cu): Land et al. (1992), Nagashima et al. (1993) Xuesong Li et al. (2009) Thermal decomposition of SiC: van Bommel et al. (1975), Forbeaux et al. (1998) GRAPHITE Chemical methods Mechanical exfoliation Graphite Intercalated Compounds (GIC) Novoselov et al (2004) Scotch tape method 26

27 Graphite Oxide (GO) Decomposed resulting carbon from a GIC with acids, metal oxisalts Highly oxydized layers are corrugated, non conductive Brodie (1860) Hummers & Offemann (1956) Staudenmeier (1898) KClO3/HNO3 KMnO 4 /H 2 SO 4 KClO3/H2SO4 EXFOLIATION by subit HT Expanded d Graphite 27

28 Graphene Oxide and Graphene Intercalation + oxidation Natural Graphite Hummers GO Exfoliation Ultrasonication Stankovich et al. Carbon (2007) Complete exfoliation not possible. Low yield Exfoliated Graphene Oxide Reduction hydrazine Separation Exfoliated Graphene Oxide from Exfoliated Graphite Oxide by ultracentrifugation Graphene 28

29 New aproaches-cnt unzipping Terrones, ACS Nano (2010) Jiao et al, Nature (2009) Kosynkin et al, Nature (2009) Cano-Márquez et al, Nano Lett (2009) Elías et al, Nano Lett (2010) Kim et al, ACS Nano (2010) 29

30 What is GRAnPH Conventional GRAPHITE GRAnPH HELICAL-RIBBON CNF New aproach CNT Stankovich et al, Varela-Rizo et al, Kosynkin et al, Carbon (2007) Carbon (2010) Nature (2009) 30

31 What is GRAnPH CARBON NANOFIBERS (GANF) KMnO 4 /H 2 SO 4 GRAPHENE OXIDE (GRANPH) GRAnPH is graphene nanoplatelets produced by chemical oxidation from HR-CNF 31

32 How is GRAnPH produced Chemical oxidation (unzipping the GANF CNFs) + sonication (exfoliation) GANF Modified d Hummers GO Sonication KMnO 4 /H 2 SO 4 Exfoliation GRAnPH oxide High yield Main advantages: Mass production of single/few layers graphene nanoplatelets High crystalinity Large flake area(>10 microns 2 ) Reduced GRAnPH Reduction 32

33 How is GRAnPH produced 33

34 GRAnPH -TEM 34

35 GRAnPH -TEM 35

36 GRAnPH -AFM 36

37 GRAnPH - XPS GANF C=C C-O GRAnPH oxide C=C Reduced GRAnPH C-O, epoxy C=O COOH Contribution red green magenta brown C-O ether, epoxi, COOH, Bond C - C aromatic hydroxyl C=O, carbonyl carboxylic GANF GRAnPH Oxide Reduced GRAnPH

38 GRAnPH - XPS 38

39 GRAnPH products GRAnPH oxide suspensions Solvents: Water Acetone THF Isopropanol GRAnPH Chemically reduced GRAnPH Thermally reduced 39

40 GRAnPH products GRAnPH oxide suspensions are highly stable at many solvents (no surfactant) Chemically reduced GRAnPH only in water (with NH 3 ) Or surfactants are required (not assured individual layers) 40

41 High performance in epoxy 41

42 High performance in epoxy 42

43 High performance in epoxy Mode I Fracture toughness For monotonic loading, a critical value of the stress intensity factor, termed fracture toughness (KIc) is a material property that describes the resistance to fracture. GIc, or critical strain energy release rate, is a parameter indicative of the energy required to fracture the material. Fracture energy must be balanced by energy dissipation (i.e., formation of new surfaces, plasticity, fiber pull out, rupture, bridging, g, etc.) 43

44 High performance in epoxy Mode I Fracture toughness 44

45 High performance in epoxy 45

46 High performance in epoxy 46

47 High performance in epoxy Fatigue Life 47

48 High performance in epoxy 48

49 High performance in epoxy 49

50 Thank you for your attention 50

Wafer-scale fabrication of graphene

Wafer-scale fabrication of graphene Sten Vollebregt, MSc Delft University of Technology, Delft Institute of Mircosystems and Nanotechnology Delft University of Technology Challenge the future Delft University