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Nanocomposite Fibers
Project No: M00-MD08 (formerly M00-D08)
Investigators: Yong K. Kim (Leader), A. F. Lewis, S. B. Warner, P. K. Patra
P. D. Calvert
Graduate Students: Shamal K. Mhetre and Ceyhan Celik
ABSTRACT
During the last two years, studies on the creation of nanocomposite fibers has been approached from: (1) mixing of
nanoparticles in polymer solutions, (2) polymer melt blending (compounding) of nanoparticles into fiber forming
polymers, (3) in situ polymerization of monomer/nanoparticle mixtures as well as in situ formation of nanoparticle
entities in the polymer structure and (4) study on the use of ultrasonic methods to disperse nanoparticle (especially
carbon nanotubes - CNT) into individual particulate species. It was found that traditional polymer melt blending
techniques for the creation of CNT containing nylon and polybutyleneterephthalate (PBT) fiber producing polymers
were not successful. Poor particle dispersion and weak fibers result. Mixing of nanoparticles in polymer solutions
also resulted in improper dispersion when polymer solvent is evaporated after ultrasonication. However, promising
results were achieved using in-situ polymerization of Nylon 6 under the presence of Carbon Nanotubes and
sonication treatment before polymerization. Dispersion was found to be very good compared to previously prepared
fibers from melt blending CNTs in fiber grade nylon 66 and PBT polymer. Here some concentrates of 20%
carbon (multiwall) nanotubes in nylon 66 and polybutylene terephthalate (PBT) were used. Studies on electrical
properties of nanocomposites show that particle size and shape, mixing time, filler concentration, composite
processing technique, and filler/matrix interactions are significant factors, affecting the electrical resistance of CNT
nanocomposites.
OBJECTIVE
The objective of this research is to explore the structure, properties, and processing of fibers that contain nanoscale
embedded hard particles. The particles may be another polymer, ceramic, metal, carbon nanotubes, or graphite, but
they must be on the size scale of nanometers in dimension. Hence, a large portion of the composite fiber is
effectively interfacial material in which the two phases are intimately blended. This should provide the fibers with
unique structure and properties.
INTRODUCTION
Nanocomposites are a distinct form of composite materials, which involve imbedding nano or molecular domain
sized particles into organic polymer, metal or ceramic matrix materials. In all cases, it is perceived that the intimate
inclusion of these nanoparticles in these matrices can completely change the properties of these materials. The
nanoparticles can serve as matrix reinforcement as well as change the electrical behavior of these base materials.
The reason for this is that with such small inclusions, a large amount of interfacial phase material is now included in
the bulk of these nanocomposites. A complete transformation of the materials chemical, mechanical and
morphological domain structure can be achieved by the proper addition of nanoparticles.
Figure 1. Polarized Light Microscope Image of CNT/Nylon 66 (CNT 4%) Extruded Fiber by Melt Mixing.
Figure 2. Polarized Light Microscope Image of CNT/Nylon 6 (CNT 1%) Fiber prepared by In-situ Polymerization
Technique.
and modulus of fibers. We believe that following is the mechanism that contributes to a good dispersion of carbon
nanotube in fibers prepared by in-situ technique. Figure 3 and Figure 4 shows the chemical structure of monomer caprolactam and single wall carbon nanotube respectively.
Mesh
140-325
60-140
40- 60
Micrometer
44-105
105-250
250-500
We use expanded natural flake graphite, supplied from Asbury Carbons Inc. Expanded Graphite (EG) is a material
of scientific and industrial interest. It is produced by exfoliation of graphite intercalation compounds. Graphite can
react with both oxidizers and reducers [3]. When they are going to be combined with polymers, expandable graphite
particles are usually mixed and saturated with oxidizers and the intercalants. A mixture of acids (concentrated
sulfuric acid and concentrated nitric acid) and graphite is the usual recipe for graphite intercalation compounds,
GICs [4]. The nitric acid serves as an oxidizer and the sulfuric acid serves as an intercalant [5]. The process,
through rapid heating of a GIC, induces vaporization and dislocation of the intercalated species. If the pressures of
the gasified intercalate increases excessively on heat treatment of GICs, a significant expansion along the c-axis
takes place as shown in Figure 5. Expansion of graphite results in many pores of different sizes ranging from 10 nm
to 10 micrometer. It has a loose vermicular structure and a very low density in the range of 3-10 kg/m3 [5, 6, 7].
(a)
(b)
Figure 5. SEM Photomicrographs of (a) Natural Flake Graphite, (b) Expanded Graphite Showing Abundant
Multi-Pores.
The expanded graphite was melt blended with Noryl, a modified PPE/PS blend (General Electric Plastics), in a
Brabender mixer. The mixing was carried out at 275C, using a screw speed of 30 rpm for 10 minutes. The
specimens were prepared in a compression molding machine, and their surface resistivity was measured on 1cm2
area specimens using a Mahlo Control Systems, DMB-10 Textometer.
Table 2. Surface Resistivity of EG filled Noryl.
Graphite Size Range
250-400m
Sample
Designation
105-250m
44-105m
10 wt%
5 wt%
2 wt%
1 wt%
10 wt%
5 wt%
1 wt%
10 wt%
5 wt%
1 wt%
Surface Resistance
()
1.0x104
4.2x109
7.8x1011
---*
8.2x107
---*
---*
9.1x108
---*
---*
* Resistance above 1012 could not be measured because of the limitations of the testing device.
The results show that, the surface resistance of EG filled samples at 10 % loading of expanded graphite decreases as
the particle size increases.
3. Functionalization of Carbon Nanotubes
(a) Carboxylic Functionalization Using Acid Treatments
This experiment consisted of treating raw, as prepared carbon nanotubes with concentrated nitric acid (HNO3) and
sulphuric acids. Figure 6 describes the reaction involved in this process
OH
H2SO4/HNO3
HO
O
HO
HO
O
HO
FUTURE CONSIDERATIONS
Prepared nylon 6 \ carbon nanotube nanocomposite will be examined critically with transmission electron
microscopy (TEM) for polymer-nanotube interaction and nanotube dispersion in polymer matrix.
Comparison in mechanical properties of prepared neat fibers and films and those of nanocomposites will be done
using Instron and nondestructive ultrasonic inspection system.
The electrical resistance of graphite embedded nanocomposites will be quantified and the significance of each
parameter e.g. particle size and shape, mixing time on filler distribution, filler concentration, composite processing
technique, and filler/matrix interactions will be examined.
REFERENCES
1. R. Saito, G. Dresselhaus, M. S. Dresselhaus, Physical Properties of Carbon Nanotubes, Imperial College Press,
London, U. K. (1998)
2. Thomas Tiano, Margaret Roylance, John Gassner, Functionalization Of Single-Wall Nanotubes For Improved
Structural Composites, Proceedings of 32nd International SAMPE Technical Conference, November 5-9, 2000,
Boston, MA
3. Hari Singh Nalwa; Handbook of Organic Conductive Molecules and Polymers, Volume 1, Charge-Transfer Slats,
Fullerenes and Photoconductors; John Wiley & Sons, 1997.
4. Xiao-Mei Chen, Jing-Wei Shen, Wen-Yi Huang; Novel electrically conductive polypropylene/graphite
nanocomposites; Journal of Materials Science Letters, 21, 2002,213-214.
5. Guo-Hua Chen, Da-Jun Wu, Wen-Gui Weng, Wen-Li Yan; Dispersion of Graphite Nanosheets in a Polymer
Matrix and the Conducting Property of the Nanocomposites; Polymer Engineering and Science, Vol 41, No.12,
December 2001.
6. Wenge Zheng, Shing-Chung Wong, Hung-Jue Sue; Transport Behaviour of PMMA/expanded graphite
nanocomposites; Polymer, 73, 6767-6773, 2002.
7. Guo-Hua Chen, Preparation of polystyrene-graphite conducting nanocomposites via intercalation polymerization;
Polymer International, 50, 980-985, 2001.
Website: http://www.umassd.edu/engineering/textiles/research/nanocompositefibers_files/frame.htm