Electro-mechanical properties of triblock copolymer styrene-butadiene-styrene / carbon nanotube composites for large deformation sensor applications

Thermoplastic elastomer/carbon nanotube composites are studied for sensor applications due to their excellent mechanical and electrical properties. Piezoresisitive properties of tri-block copolymer styrene-butadiene-styrene (SBS)/ carbon nanotubes (CNT) prepared by solution casting have been investigated. Young modulus of the SBS/CNT composites increases with the amount of CNT filler content present in the samples, without losing the high strain deformation on the polymer matrix (~1500 %). Further, above the percolation threshold these materials are unique for the development of large deformation sensors due to the strong piezoresistive response. Piezoresistive properties evaluated by uniaxial stretching in tensile mode and 4-point bending showed a Gauge Factors up to 120. The excellent linearity obtained between strain and electrical resistance makes these composites interesting for large strain piezoresistive sensors applications.

Hydroxyapatite-nanotube composites and coatings for orthopedic applications

Hydroxyapatite (HA) has received wide attention in orthopedics, due to its biocompatibility and osseointegration ability. Despite these advantages, the brittle nature and low fracture toughness of HA often results in rapid wear and premature fracture of implant. Hence, there is a need to improve the fracture toughness and wear resistance of HA without compromising its biocompatibility. ^ The aim of the current research is to explore the potential of nanotubes as reinforcement to HA for orthopedic implants. HA- 4 wt.% carbon nanotube (CNT) composites and coatings are synthesized by spark plasma sintering and plasma spraying respectively, and investigated for their mechanical, tribological and biological behavior. CNT reinforcement improves the fracture toughness (>90%) and wear resistance (>66%) of HA for coating and free standing composites. CNTs have demonstrated a positive influence on the proliferation, differentiation and matrix mineralization activities of osteoblasts, during in-vitro biocompatibility studies. In-vivo exposure of HA-CNT coated titanium implant in animal model (rat) shows excellent histocompatibility and neobone integration on the implant surface. The improved osseointegration due to presence of CNTs in HA is quantified by the adhesion strength measurement of single osteoblast using nano-scratch technique. ^ Considering the ongoing debate about cytotoxicity of CNTs in the literature, the present study also suggests boron nitride nanotube (BNNT) as an alternative reinforcement. BNNT with the similar elastic modulus and strength as CNT, were added to HA. The resulting composite having 4 wt.% BNNTs improved the fracture toughness (∼85%) and wear resistance (∼75%) of HA in the similar range as HA-CNT composites. BNNTs were found to be non-cytotoxic for osteoblasts and macrophages. In-vitro evaluation shows positive role of BNNT in osteoblast proliferation and viability. Apatite formability of BNNT surface in ∼4 days establishes its osseointegration ability.^

Tin oxide based composites derived using electrostatic spray deposition technique as anodes for lithium-ion batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200, 250, 300 °C) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 °C deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 °C exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 °C showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2–74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Tin Oxide Based Composites Derived Using Electrostatic Spray Deposition Technique as Anodes for Li-Ion Batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Effect of butadiene/styrene ratio, block structure and carbon nanotube content on the mechanical and electrical properties of thermoplastic elastomers after UV ageing

Thermoplastic elastomers based on a triblock copolymer styrene-butadiene-styrene (SBS) with different butadiene/styrene ratios, block structure and carbon nanotube (CNT) content were submitted to accelerated weathering in a Xenontest set up, in order to evaluate their stability to UV ageing. It was concluded that ageing mainly depends on butadiene/styrene ratio and block structure, with radial block structures exhibiting a faster ageing than linear block structures. Moreover, the presence of carbon nanotubes in the SBS copolymer slows down the ageing of the copolymer. The evaluation of the influence of ageing on the mechanical and electrical properties demonstrates that the mechanical degradation is higher for the C401 sample, which is the SBS sample with the largest butadiene content and a radial block structure. On the other hand, a copolymer derivate from SBS, the styrene-ethylene/butadiene-styrene (SEBS) sample, retains a maximum deformation of ~1000% after 80 h of accelerated ageing. The hydrophobicity of the samples decreases with increasing ageing time, the effect being larger for the samples with higher butadiene content. It is also verified that cytotoxicity increases with increasing UV ageing with the exception of SEBS, which remains not cytotoxic up to 80 h of accelerated ageing time, demonstrating its potential for applications involving exposition to environmental conditions.

Monitoramento de danos estruturais utilizando sensores de nanocompósitos

Pós-graduação em Engenharia Mecânica - FEIS

Modeling Carbon Nanotube Electrical Properties in CNT/Polymer Composites

In this work it is demonstrated that the capacitance between two cylinders increases with the rotation angle and it has a fundamental influence on the composite dielectric constant. The dielectric constant is lower for nematic materials than for isotropic ones and this can be attributed to the effect of the filler alignment in the capacitance. The effect of aspect ratio in the conductivity is also studied in this work. Finally, based on previous work and by comparing to results from the literature it is found that the electrical conductivity in this type of composites is due to hopping between nearest fillers resulting in a weak disorder regime that is similar to the single junction expression.

Mechanical Properties and Durability of CNT Cement Composites

In the present paper, changes in mechanical properties of Portland cement-based mortars due to the addition of carbon nanotubes (CNT) and corrosion of embedded steel rebars in CNT cement pastes are reported. Bending strength, compression strength, porosity and density of mortars were determined and related to the CNT dosages. CNT cement paste specimens were exposed to carbonation and chloride attacks, and results on steel corrosion rate tests were related to CNT dosages. The increase in CNT content implies no significant variations of mechanical properties but higher steel corrosion intensities were observed.

Brittle and ductile removal modes observed during diamond turning of carbon nanotube composites

Ultraprecision diamond turning was used to evaluate the surface integrity of a carbon nanotube (CNT) composite as a function of the cutting conditions and the percentage of CNT in the epoxy matrix. The effects of cutting conditions on the chip morphology and surface roughness were analysed. The results showed that an increase in the percentage of CNT may influence the mechanism of material removal and consequently improve the quality of the machined surface. When smaller quantities of CNT (0.02 and 0.07 wt %) are present in the matrix, microcracks form within the cutting grooves (perpendicular to the cutting direction). This indicates that the amount of CNT on the epoxy matrix may have a direct influence on the mechanical properties of these materials. Chips removed from the CNT composite samples were analysed by scanning electron microscopy in order to correlate the material removal mechanism and the surface generation process. The area average surface roughness Sa was influenced by the material removal mechanism (Sa ranging from 0.28 to 1.1 mu m).

Coupling Mechanical and Electrical Behavior in the Multi-scale Simulation of Polymer-based CNT Nanocomposites

A numeric model has been proposed to investigate the mechanical and electrical properties of a polymeric/carbon nanotube (CNT) composite material subjected to a deformation force. The reinforcing phase affects the behavior of the polymeric matrix and depends on the nanofiber aspect ratio and preferential orientation. The simulations show that the mechanical behavior of a computer generated material (CGM) depends on fiber length and initial orientation in the polymeric matrix. It is also shown how the conductivity of the polymer/CNT composite can be calculated for each time step of applied stress, effectively providing the ability to simulate and predict strain-dependent electrical behavior of CNT nanocomposites.

Microinjection molding of polyamide 6/carbon nanotube composites

Microinjection molding of polymer composites with carbon nanotubes (CNT) requires previous production of the nanocomposites, often by melt extrusion. Each processing step has a thermo-mechanical effect on the polymer melt, conveying different properties to the final product. In this work, polyamide 6 and its composites with pristine and functionalized CNT (f-CNT) were processed by a mini twin-screw extrusion, followed by microinjection molding. The morphology induced on the polymer by each process was analyzed by differential scanning calorimetry and wide angle X-ray diffraction. Calorimetric analysis showed a secondary crystallization for the microinjected materials, absent for the extruded materials. The characterization of microinjected polyamide 6 by X-ray diffraction revealed a large contribution of the c phase to the total crystallinity, mainly in the skin region, while the nanocomposites and extruded materials were characterized by a larger contribution of the a phase. Functionalization of CNT did not affect significantly the polymer morphology compared to composites with pristine CNT.

Mechanical vs. electrical hysteresis of carbon nanotube/styrene-butadiene-styrene composites and their influence in the electromechanical response

The interesting properties of thermoplastics elastomers can be combined with carbon nanotubes (CNT) for the development of large strain piezoresistive composites for sensor applications. Piezoresistive properties of the composites depend on CNT content, with the gauge factor increasing for concentrations around the percolation threshold, mechanical and electrical hysteresis. The SBS copolymer composition (butadiene/styrene ratio) influences the mechanical and electrical hysteresis of composites and, therefore, the piezoresistive response. This work reports on the electrical and mechanical response of CNT/SBS composites with 4%wt nanofiller content, due to the larger electromechanical response. C401 and C540 SBS copolymers with 80% and 60% butadiene content, respectively have been selected. The copolymer with larger amount of soft phase (C401) shows a rubber-like mechanical behavior, with mechanical hysteresis increasing linearly with strain until 100% strain. The copolymer with the larger amount of hard phase (C540) just shows rubber-like behavior for low strains. The piezoresistive sensibility is similar for both composites for low strains, with a GF≈ 5 for 5% strain. The electrical hysteresis shows opposite behavior than the mechanical hysteresis, increasing with strain for both composites, but with higher increase for softer copolymer, C401. The GF increases with increasing strain, but this increase is larger for composites with lower amounts of soft phase due to the distinct initial modulus and deformation of the soft and hard phases of the copolymer. The soft phase shows larger strain under a given stress than the harder phase and the conductive pathway rearrangements in the composites are different for both phases, the harder copolymer (C540) showing higher piezoresistive sensibility, GF≈ 18, for 20% strain.

Microstructure and mechanical properties of carbon nanotube reinforced cementitious composites developed using a novel dispersion technique

The authors also acknowledge Centre for Textile Science and Technology (University of Minho) and FIBRENAMICS PLATFORMfor providing required conditions for this research. Sincere thanks are also due to Mr. Pedro Samuel Leite and Mr. Carlos Jesus for their kind help in sample preparation and testing.

Carbon nanotubes/polyamide 6.6 nanostructured composites crystallization kinetic study

Compared with the traditional composites, the incorporation of carbon nanotubes into polymeric matrices can generate materials with superior properties, especially thermal, electrical and tribological properties. The aim of this study was to study the polyamide 6.6/carbon nanotubes (PA 6.6/CNT) nanostructured composites crystallization kinetics. The solution mixing technique was used to obtain the nanostructured composites studied in this work. PA 6.6 films were produced with amounts of 0.1, 0.5, and 1.0 wt% (weight/weight) CNT. X-ray diffraction analyses were performed in order to determine the crystallographic properties of nanostructured composite. The nanostructured composites crystallization kinetic study was performed using the differential scanning calorimetry under isothermal and nonisothermal (dynamic) conditions. The results have shown addition of CNTs in the PA 6.6 reduces the Avrami exponent, affecting the crystallization process of the composite. © The Author(s) 2012.

Nanostructured Composites Based on Carbon Nanotubes and Epoxy Resin for Use as Radar Absorbing Materials

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)