1. 1 The Development of Mechanically & Electrically CNF & CNF Reinforced Composite Imran Syakir Mohamad

2. 2 Objective To develop high mechanically & electrically CNF and CNF reinforced composite using various substrates and catalysts

3. 3 Scope To identify and evaluate several type of commercially available substrate Inorganic-based (carbon cloth, fiberglass, silica, etc) Plastic-based (polystyrene, nylon, polypropylene, etc) To develop catalysts for carbon-growth process (cracking of carbon-carbon bond) 3 monometallic catalysts 2 bimetallic catalysts

4. 4 Scope To develop methodology for grafting of catalyst onto the substrate Identify suitable metal salt solution or metal Condition of grafting for: Deposition method (pH, temperature, concentration) Sputtering method (radio frequency, time) To grow nanocarbon onto the catalyst grafted substrate using a few technique FCCVD PECVD

5. 5 Scope All samples will be characterized for their: Compositional Analysis (EDX, XRF) Morphology/Structure Analysis (FESEM, HRTEM) Texture/Surface Area Analysis (BET) Functionality (Raman, UV-Vis) Mechanical & Electrical Properties Analysis

6. 6 Applications Energy storage Have intrinsic properties. Can be used as an electrode in batteries & capacitor Very high surface area Good electrical conductivity Their linear geometry makes their surface highly accessible to the electrolyte Use as gases and ions transport media

7. 7 Applications Air, Water and Gas Filtration these filters can not only block the smallest particles but also kill most bacteria Structural composite Good mechanical properties, such as stiffness, toughness, strength and lightweight. Possible to replace commercial fiber (e.g.Fiberglass) COMMERCIAL AIR FILTRATION CARTRIDGE USING NANOFIBER FILTER MEDIA

8. 8 Challenges Economic & reasonable cost, high production Well homogeneous catalyst dispersion Strong vertical align CNF attachment onto the substrate (inside the pore) Enhance CNF properties (mechanical, electrical, thermal) Control the CNF characteristic (diameter, length)

9. 9 Substrate Proposed: Inorganic-based (Carbon Cloth) Plastic-based (Polypropylene)

10. 10 Carbon Cloth as a Substrate Reason High microporosity High surface area (>1000 m 2 /g) Excellent adsorbent in gas & liquid media Well establish/commercial Narrow fiber diameter (10-20 micron) Offer more catalytic property Offer more adsorption ability

11. 11 Carbon Cloth E-TEK CC Specifications Weave = Plain Weight = 116 g/m 2 Thickness = 0.35 mm Size = 25 cm x 25 cm Content = 99 % carbon, 1 % ash Price = $43.75

12. 12 Catalyst Proposed (FCCVD) 3 monometallic: Fe, Ni, Co metallocene as a catalyst precursors Ferrocene Nickelocene Cobaltocene 2 bimetallic which are combination of two monometallic Fe-Co Ni-Fe FeNiCo

13. 13 Metallocene as Catalyst Precursor Why choose metallocene? Catalyst size – main important for CNF formation. Nanosize cat. particles  catalyze CNF growth Metallocene chosen because easy to vaporize at lower temp. (faster & simple process) Vaporize metallocene molecule carried to reaction tube by H 2 gas and C 2 H 4. Reduce by H 2 to form Fe atom & deposite onto substrate.

14. 14 Catalyst Proposed (PECVD) 3 monometallic: Fe, Ni, Co Metal salt as a precursors Iron nitrate, Fe Nickel nitrate, Ni(NO 3 ) 2.6H 2 O Cobalt nitrate, Co 2 bimetallic which are combination of two monometallic Fe-Co Ni-Fe

15. 15 Technique Proposed FCCVD Floating Catalyst Chemical Vapor Deposition Best for high productivity High potential application in industry PECVD Plasma Enhanced Chemical Vapor Deposition Best to synthesize vertical aligned CNF Low temperature deposition PECVD

16. 16 Experimental Route (FCCVD) Washing (removes impurities; eg: Al, Si, Fe, K) Washing (removes impurities; eg: Al, Si, Fe, K) Catalyst Development Nanocarbon Growth Characterization Monometallic Bimetallic Monometallic Bimetallic Compositional analysis (EDX,XRF) Morphology/Structure analysis (SEM, HRTEM) Texture/Surface Area analysis (BET) Functionality (Raman) Mechanical & Electrical Properties Analysis Compositional analysis (EDX,XRF) Morphology/Structure analysis (SEM, HRTEM) Texture/Surface Area analysis (BET) Functionality (Raman) Mechanical & Electrical Properties Analysis Carbon source (C 2 H 4 ) Carrier gas (H 2 & N 2 ) Additive (Thiophene, H 2 S) Carbon source (C 2 H 4 ) Carrier gas (H 2 & N 2 ) Additive (Thiophene, H 2 S) Substrate (CC) Substrate (CC) Treatment CNF CNF After Treatment Polymer (PP) CNF Reinforced treat with HNO 3, T=30 o C, 24 hr wash with deionized water (1L), dried T=200 o C, 2 hr treat with HNO 3, T=30 o C, 24 hr wash with deionized water (1L), dried T=200 o C, 2 hr Use acid treatment (HCl) to remove catalyst & amorphous C.

17. 17 Setup (FCCVD) Schematic Diagram of a FCCVD system Heating coil Catalyst Furnace Substrate H2H2 N2N2 Outlet Stainless steel tube C2H4C2H4 Mass flow meter Thiophene

18. 18 Growth Condition (FCCVD) ProcessCalcinationReductionGrowthCooling SourcesN2N2 N 2 +H 2 H 2 +C 2 H 4 N2N2 Temp250 o C300 o C600 o CRT Composition5% N 2 20% C 2 H 4 Time1 hr 2 hrs To enhanced the catalytic activity Catalyst deposition Idea: Replace H 2 with NH 3. WHY?

19. 19 Aligned CNT was obtained in NH3 and N2 environment Synthesis condition CNT Morphology Citation method Temperatue( o C)Reaction GasCatalyst PE-CVD666C 2 H 2 +NH 3 NiAligned CNTScience 282, 1105 (1998) PE-CVD660C 2 H 2 +NH 3 NiAligned CNTAPL 75 1086 (1999) PE-CVD825C 2 H 2 +NH 3 CoAligned CNTAPL 77 830 (2000) Thermal-CVD750~950C 2 H 2 +NH 3 FeAligned CNTAPL 77 3397 (2000) PE-CVD825C 2 H 2 +NH 3 CoAligned CNTAPL 77 2767 (2000) Thermal-CVD800C 2 H 2 +NH 3 FeAligned CNTAPL 78 901 (2001) Thermal-CVD 950C 2 H 2 +NH 3 Ni, Co Aligned CNT TSF 398-399 150 (2001) 850 C 2 H 2 +H 2, C 2 H 2 +N 2 Tangled CNT Thermal-CVD 950C 2 H 2 +NH 3 Ni Aligned CNT DRM 10 1235 (2001) 950C 2 H 2 +H 2, C 2 H 2 +N 2 Tangled CNT Thermal-CVD 800~900C 2 H 2 +NH 3 Ni Aligned CNT JAP 91 3847 (2002) 600~900C 2 H 2 +H 2 Tangled CNT PE-CVD660<C 2 H 2 +NH 3 NiAligned CNTAPL 80 4018 (2002) Thermal-CVD850~900C 2 H 2 +ArNi, CoTangled CNTAPL 75 1721 (1999) PE-CVD500CH 4 +N 2 Fe, NiAligned CNTAPL 75 3105 (1999) PE-CVD550CH 4 +N 2 FeAligned CNTJAP 89 5939 (2001) PE-CVD700CH 4 +H 2 NiAligned CNTAPL 76 2367 (2000) Thermal-CVD800ferrocene+xylene Fe Aligned CNTAPL 77 3764 (2000) But why?

20. 20 Ni particles after pretreatment for 1h… Activated Nitrogen 300nm In H 2 +N 2 In pure NH 3 Activated Nitrogen plays a significant role in vertically aligned CNT growth

21. 21 NH 3 H2H2 H2H2 H2H2 PretreatmentReaction Role of activated nitrogen during CNT growth?

22. 22 Pretreatment in NH 3 environment was neither a sufficient nor necessary for vertically aligned CNT growth There are some relationship between nitrogen concentration in CNT and CNT growth rate Nitrogen is chemically bonded with carbon atoms in graphite basal plane Enhanced CNT growth in an NH3 environment is due to nitrogen incorporation into the CNT wall or cap.

23. 23 Experimental Route (PECVD) Washing (removes impurities; eg: Al, Si, Fe, K) Washing (removes impurities; eg: Al, Si, Fe, K) Catalyst Development Nanocarbon Growth Characterization Monometallic Bimetallic Monometallic Bimetallic Compositional analysis (EDX,XRF) Morphology/Structure analysis (SEM, HRTEM) Texture/Surface Area analysis (BET) Functionality (Raman) Mechanical & Electrical Properties Analysis Compositional analysis (EDX,XRF) Morphology/Structure analysis (SEM, HRTEM) Texture/Surface Area analysis (BET) Functionality (Raman) Mechanical & Electrical Properties Analysis Carbon source (C 2 H 4 ) Carrier gas (H 2, N 2, NH 3 ) Carbon source (C 2 H 4 ) Carrier gas (H 2, N 2, NH 3 ) Substrate (CC) Substrate (CC) Treatment Impregnation CNF CNF After Treatment Polymer (PP) CNF Reinforced treat with HNO 3, T=30 o C, 24 hr wash with deionized water (1L), dried T=200 o C, 2 hr treat with HNO 3, T=30 o C, 24 hr wash with deionized water (1L), dried T=200 o C, 2 hr Cat. + deionized water + acetone under ultrasonic, 30 min, 25 o C (water bath) aging 12 hr, 60 o C Cat. + deionized water + acetone under ultrasonic, 30 min, 25 o C (water bath) aging 12 hr, 60 o C Use acid treatment (HCl) to remove catalyst & amorphous C.

24. 24 Setup (PECVD) Schematic Diagram of a PECVD system

25. 25 Growth Condition (PECVD) ProcessPretreatmentGrowth SourcesN 2 +H 2 NH 3 +C 2 H 4 Parameter (T,t,P,%, etc) Will be determine later To enhanced the catalytic activityVertical align CNF induce by plasma electric field

26. 26 CNF Reinforced Composite Polymer (PP) blending process with CNF. Enhanced the electrical and mechanical properties, light weight Plastic itself is insulator. Plastic is fragile when expose to high temp, sunlight. Commercial fiber are heavy. CNF will reduce weight and cost efficiency (low fuel) if use in vehicle body part.

27. 27 PP Polypropylene (polypropene) or (C 3 H 6 ) n Semi-rigid, good chemical resistance, tough, good fatigue resistance, good heat resistance, non toxic Cheap Density = 0.95 g/cm 3 Melting point = 173 o C Chosen because PP is a linear polymer that can contribute to the development of highly aligned nanofiber system

28. 28 Blending Process CNF Spinning Process Temp = 285 o C Speed Rotor= 600 rpm Time = ?min Temp = 285 o C Speed Rotor= 600 rpm Time = ?min Melt Blend Temp = 170-180 o C Speed Rotor = 30 rpm Time = 5-10 min Temp = 170-180 o C Speed Rotor = 30 rpm Time = 5-10 min Polypropylene CNF Reinforced

29. 29 CNF are expected to be produced with below criteria : Vertically align Strong attachment onto substrate Improved mechanically & electrically properties CNF-polymer reinforced composite are expected to be produced with below criteria: Light weight Good mechanical & electrical properties Conclusion