1. Materials CNT

2. Table of Contents Introduction Potential Applications Properties Functionalized CNTs Property Data for Specific Materials

3. Introduction

4. Scientists have been trying to use the phenomenal mechanical properties of multiwalled carbon nanotubes (MWNT) to create high performance nanocomposites, since their discovery in 1991. The properties of the MWNT’s suggest that significant improvements should be added to the mechanical properties of the polymer matrix, which they reinforce.

5. Introduction To alter the properties, strength, stiffness, permeability, optical clarity and electrical conductivity of the nanocomposites consistently two things need to occur: – the MWNT’s need to be dispersed homogeneously throughout the matrix material, and there needs to be good interfacial bonding between the MWNT’s and the polymer matrix material.

6. Introduction Strong bonding at the interface is required to transfer the load from the polymer material to the reinforcing MWNT. This can be achieved if the surface energy of the CNT exceeds the cohesive energy of the polymer matrix. Weak interfacial bonding will result in de- lamination giving instant mechanical failure.

7. Introduction Weak interfacial bonding is a result of a non- wetting phenomenon between the CNT and polymer matrix, which is caused by the lack of functional groups on the CNT’s.

8. Introduction There are two styles of polymer treatments for CNT’s: – wrapping and non-wrapping. Polymer wrapping means the treating polymer completely envelops the CNT surface.

9. Introduction Non-wrapping polymer treatments are where the polymer backbone extends along the length of the CNT without any portion of the polymer treatment covering more than half of the diameter of the CNT. Non-wrapping polymer treatments contain a rigid backbone, which results in parallel stacking phenomena between the polymer and the CNT.

10. Introduction The addition of treatments to the surface of the nanotubes is being researched and is intended to improve dispersion during processing, such as injection molding. These treatments consist of functionalizing the CNT by attaching polymeric chains to its surface.

11. History 1991 Discovery of multi-wall carbon nanotubes 1992 Conductivity of carbon nanotubes 1993 Structural rigidity of carbon nanotubes 1993 Synthesis of single-wall nanotubes 1995 Nanotubes as field emitters 1996 Ropes of single-wall nanotubes 1997 Quantum conductance of carbon nanotubes 1997 Hydrogen storage in nanotubes 1998 Chemical Vapor Deposition synthesis of aligned nanotube films 1998 Synthesis of nanotube peapods 2000 Thermal conductivity of nanotubes 2000 Macroscopically aligned nanotubes 2001 Integration of carbon nanotubes for logic circuits 2001 Intrinsic superconductivity of carbon nanotubes

12. Potential Applications

13. Reinforcement within a polymeric matrix Outstanding mechanical properties – High Young’s modulus – Stiffness and flexibility – Unique electronic properties – High thermal stability The nearly perfect structure of CNTs, their small diameter, and their high surface area and high aspect ratio, provide an amazing inorganic structure with unique properties extremely attractive to reinforcing organic polymers

14. Potential Applications Tips for Atomic Force Microscopy Cells for hydrogen storage Nanotransistors Electrodes for electromechemical applications Sensors of biological molecules Catalysts Reinforcement of composite materials Semiconductor or metallic conductive nanomaterials Various aerospace applications

15. Potential Applications Flat Panel Displays – Prototypes have been made by Samsung Gas-Discharge Tubes in Telecom Networks Energy Storage Electrochemical Intercalation of Carbon Nanotubes with Lithium – CNTs can be used as the cathode to make a battery hold 3x as much charge and output 10x as much power Nanoprobes and Sensors

16. Potential Applications Use as coatings – Antistatic coatings – Flame barrier coatings – Fouling release coatings On boats to prevent marine life from adhering to the ship’s bottom

17. Potential Applications Markets EnergyElectronicsAutomotive Stuctural CompositesOthers BatteryWind Semicon and Disk Drive ITO replacement Electrostatic painting Fuel systemsAerospace Sporting goods Thermal Management Flame Retardant CNT Performance Attribute High electrical conductivityX XXXXX High thermal conductivityX X XX High tensile strengthXX XX High elasticity X XX High absorbency X X XX High aspect ratio (L/D)XXXXXXXXXX Low weight X XXXX

18. Potential Applications

19. BMC bicycle frame made of nanotube-reinforced resin, 2005 Tour de France. ARKEMA belongs to the network of partners.

20. Properties

21. When small quantities of nanotubes are incorporated into the polymer, the electrical, optical and mechanical properties improve significantly CNTs in large amounts form clusters, diminishing their interaction The Young’s modulus of the multi-walled carbon nanotubes is 0 ⋅ 9 TPa

22. Properties

23. Physical Properties of Carbon Nanotubes Below is a compilation of research results from scientists all over the world. All values are for Single Wall Carbon Nanotubes (SWNT's) unless otherwise stated. Equilibrium Structure Average Diameter of SWNT's 1.2 -1.4 nm Distance from opposite Carbon Atoms (Line 1) 2.83 Å Analogous Carbon Atom Separation (Line 2) 2.456 Å Parallel Carbon Bond Separation (Line 3) 2.45 Å Carbon Bond Length (Line 4) 1.42 Å C - C Tight Bonding Overlap Energy ~ 2.5 eV Group Symmetry (10, 10) C 5V Lattice: Bundles of Ropes of Nanotubes Triangular Lattice (2D) Lattice Constant 17 Å Lattice Parameter: (10, 10) Armchair16.78 Å (17, 0) Zigzag16.52 Å (12, 6) Chiral16.52 Å Density: (10, 10) Armchair1.33 g/cm 3 (17, 0) Zigzag1.34 g/cm 3 (12, 6) Chiral1.40 g/cm 3 Interlayer Spacing: (n, n) Armchair3.38 Å (n, 0) Zigzag3.41 Å (2n, n) Chiral3.39 Å. Optical Properties Fundamental Gap: For (n, m); n-m is divisible by 3 [Metallic]0 eV For (n, m); n-m is not divisible by 3 [Semi-Conducting]~ 0.5 eV Electrical Transport Conductance Quantization (12.9 k )-1 Resistivity 10 -4 -cm Maximum Current Density 10 13 A/m 2. Thermal Transport Thermal Conductivity ~ 2000 W/m/K Phonon Mean Free Path ~ 100 nm Relaxation Time ~ 10 -11 s. Elastic Behavior Young's Modulus (SWNT) ~ 1 TPa Young's Modulus (MWNT) 1.28 TPa Maximum Tensile Strength ~ 100 GPa

24. Mechanical Properties of Engineering Fibers Fiber MaterialSpecific DensityE (TPa)Strength (GPa)Strain at Break (%) Carbon Nanotube1.3 - 2110-6010 HS Steel7.80.24.1< 10 Carbon Fiber - PAN1.7 - 20.2 - 0.61.7 - 50.3 - 2.4 Carbon Fiber - Pitch2 - 2.20.4 - 0.962.2 - 3.30.27 - 0.6 E/S - glass2.50.07 / 0.082.4 / 4.54.8 Kevlar* 491.40.133.6 - 4.12.8 Kevlar is a registered trademark of DuPont. Properties

25. Table 2. Transport Properties of Conductive Materials MaterialThermal Conductivity (W/m.k)Electrical Conductivity Carbon Nanotubes> 3000106 - 107 Copper4006 x 107 Carbon Fiber - Pitch10002 - 8.5 x 106 Carbon Fiber - PAN8 - 1056.5 - 14 x 106 Properties

27. Electrical conductivity: Carbon nanotubes are conductors or semiconductors, based on coiling helicity. Their conductivity ranges from 1 S/cm to 100 S/cm. This property has been calculated and verified in experiments. Thermal conductivity: Carbon nanotubes feature thermal conductivity close to that of diamond (3000 J/K), the best thermal conductor known. Mechanical performance: In the hexagon plane, the Young’s modulus for carbon nanotubes has been theoretically evaluated at 1TPa. Together with this outstanding strength, carbon nanotubes boast high flexibility and good plasticity. Adsorption: Nanotubes were first studied with the objective of becoming a means of storing hydrogen for the new fuel cells. Although this application has been gradually discarded, the fact remains that nanotubes have an empty space around the cylinder axis which can constitute a nanotank. The specific surface of nanotubes is approximately 250 m2/g, imparting good adsorption capacity.

28. Properties CNTs have been shown to possess many extraordinary properties such as strength 16X that of stainless steel and with a thermal conductivity five times that of copper. aspect ratio (length over diameter) ranges from 1,000 to 1,000,000 Electrical Resistivity: 10 -4 Ω-cm Current Density: 10 7 amps/cm 2 Thermal Conductivity: 3,000 W/mK Tensile Strength: 30 GPa Elasticity: 1.28 TPa

29. Properties

41. Nanotube Research Articles\Overall\nanotube composites.pdf Nanotube Research Articles\Overall\nanotube composites.pdf Very good article explaining the basics of CNT’s

42. Properties

47. Filling CNTs

48. CNT–Polymer Interfacial Strength

49. Effects From Size

50. Functionalized CNTs

51. Additives Additives can aid in the dispersion of the CNTs

52. Functionalized CNTs Oxidation on the surfaces of these materials are useful moieties in order to bond new reactive chains that improve solubility, processability and compatibility with other materials and, therefore, improve the interfacial interactions of CNs with other substances The most important impact has been produced by oxidation methods which, in addition to reducing impurities, cause chemical modifications of CNTs The COOH groups generated in the oxidation process are used to attach different molecules useful to improve surface compatibility of CNTs with other materials

53. Functionalized CNTs The COOH groups generated in the oxidation process are used to attach different molecules useful to improve surface compatibility of CNTs with other materials Chemical functionalization has reached an important position in the CNT field, as different chemical processes have been developed to diversify CNT properties The remarkable properties obtained when f-CNTs are incorporated into polymeric composites represent a promising route to design ideal materials for aerospace related structural applications However, the field requires much deeper fundamental research

54. Functionalized CNTs Chemical functionalized CNTs significantly decreased the electrical conductivity of epoxy nanocomposites due to unbalance polarization effect and physical structure defects due to severe condition during acidic treatment process Non chemical functionalized CNTs are more suitable for the electrical applications Chemical functionalization of CNT is still necessary for increase dispersion quality and strengthens the interfacial bonding strength with polymer matrix, which more important in structural applications

55. Functionalized CNTs

56. Functionalized CNTs (Kentera)

63. Adhesion and reinforcement in carbon nanotube polymer composite The interfacial shear stress is found to increase linearly with the applied strain in small strain regime and a lower bound value for the shear strength is found -- 46 MPa at low temperatures. Such value decreases with the increase of temperature. At large strains the interfacial bonds break successively with the shear stress decreasing in a staircase manner.

64. Adhesion and reinforcement in carbon nanotube polymer composite The mechanical properties of the composite are found to be largely enhancedover a wide temperature range from 50 to 350 K compared with the bulk polymer, due to the enhanced VDW interactions. The degree of increase in the Young’s modulus is around 200% for the composite in this study, and the difference with that from the continuum medium approximation based Halpin–Tsai formula suggests that interfacial atomic structure is crucial for a nanocomposite.

65. Adhesion and reinforcement in carbon nanotube polymer composite

66. Property Data for Specific Materials

67. PMMA Relative to pure PMMA, a 32% improvement in tensile modulus and a 28% increase in tensile strength were observed in PMMA- based nanocomposites using 1.0 wt% nanotube filler.

68. Epoxy no improvement in mechanical properties was observed in epoxy-based nanocomposites. The poorer mechanical performance of the latter system can be explained by a decrease of the crosslinking density of the epoxy matrix in the nanocomposites, relative to pure epoxy.

69. Epoxy

74. Natural Rubber

77. PVA To summarize, MWNTs have been well dispersed in PVA matrix through gum arabic treatment. The PVA/MWNT composite films exhibit good mechanical properties

78. PS

79. PBT The addition of up to 0.2 wt% MWCNT to PBT induces an increase of the microhardness of about 12%. The H values obtained are much smaller than those derived from the elastic modulus using Struik’s relation. The use of SWCNT does not improve the micromechanical properties

80. PBT

81. SBR

82. The stress value or normally known as tensile strength has been increased to 21.0% for 1 wt% of CNTs up to 70.26% for 10 wt% of CNTs The Young’s modulus or modulus of elasticity has been increased to 11.36 for 1 wt% of CNTs up to 193.91% for 10 wt% of CNTs compared to SBR without CNTs.

83. SBR

84. PC

94. PE

104. LLDPE

109. Microscope Imaging