Yadienka Martinez-Rubi

The influence of a compatibilizer on the thermal and dynamic mechanical properties of PEEK/carbon nanotube composites

The effect of polyetherimide (PEI) as a compatibilizing agent on the morphology, thermal, electrical and dynamic mechanical properties of poly(ether ether ketone) (PEEK)/single-walled carbon nanotube (SWCNT) nanocomposites, has been investigated for different CNT loadings. After a pre-processing step based on ball milling and pre-mixing under mechanical treatment in ethanol, the samples were prepared by melt extrusion. A more homogeneous distribution of the CNTs throughout the matrix is found for composites containing PEI, as revealed by scanning electron microscopy. Thermogravimetric analysis demonstrates an increase in the matrix degradation temperatures under dry air and nitrogen atmospheres with the addition of SWCNTs; the level of thermal stability of these nanocomposites is maintained when PEI is incorporated. Both differential scanning calorimetry and synchrotron x-ray scattering studies indicate a slight decrease in the crystallization temperatures of the compatibilized samples, and suggest the existence of reorganization phenomena during the heating, which are favoured in the composites incorporating the compatibilizer, due to their smaller crystal size. Dynamic mechanical studies show an increase in the glass transition temperature of the nanocomposites upon the addition of PEI. Furthermore, the presence of PEI causes an enhancement in the storage modulus, and hence in the rigidity of these systems, attributed to an improved interfacial adhesion between the reinforcement and the matrix. The electrical and thermal conductivities of these composites decrease with the incorporation of PEI. Overall, the compatibilized samples exhibit improved properties and are promising for their use in industrial applications.

Toughening of epoxy matrices with reduced single-walled carbon nanotubes

Reduced single-walled carbon nanotubes (r-SWCNT) are shown to react readily at room temperature under inert atmosphere conditions with epoxide moieties, such as those in triglycidyl p-amino phenol (TGAP), to produce a soft covalently bonded interface around the SWCNT. The soft interface is compatible with the SWCNT-free cross-linked cured matrix and acts as a toughener for the composite. Incorporation of 0.2 wt % r-SWCNT enhances the ultimate tensile strength, toughness and fracture toughness by 32, 118, and 40%, respectively, without change in modulus. A toughening rate (dK(IC)/dwt(f)) of 200 MPa m(0.5) is obtained. The toughening mechanism is elucidated through dynamic mechanical analyses, Raman spectroscopy and imaging, and stress-strain curve analyses. The method is scalable and applicable to epoxy resins and systems used commercially.

Mechanistic insights into the effect of nanoparticles on zebrafish hatch.

Abstract Aquatic organisms are susceptible to waterborne nanoparticles (NP) and there is only limited understanding of the mechanisms by which these emerging contaminants may affect biological processes. This study used silicon (nSi), cadmium selenide (nCdSe), silver (nAg) and zinc NPs (nZnO) as well as single-walled carbon nanotubes (SWCNT) to assess NP effects on zebrafish (Danio rerio) hatch. Exposure of 10 mg/L nAg and nCdSe delayed zebrafish hatch and 100 mg/L of nCdSe as well as 10 and 100 mg/L of uncoated nZnO completely inhibited hatch and the embryos died within the chorion. Both the morphology and the movement of the embryos were not affected, and it was determined that the main mechanism of hatch inhibition by NPs is likely through the interaction of NPs with the zebrafish hatching enzyme. Furthermore, it was concluded that the observed effects arose from the NPs themselves and not their dissolved metal components.

Rapid and controllable covalent functionalization of single-walled carbon nanotubes at room temperature

We report a rapid and efficient procedure to functionalize SWNT where free radicals generated at room temperature by a redox reaction between reduced SWNT and diacyl peroxide derivatives were covalently attached to the SWNT wall.

Coupled thermogravimetry, mass spectrometry, and infrared spectroscopy for quantification of surface functionality on single-walled carbon nanotubes

AbstractWe have successfully applied coupled thermogravimetry, mass spectrometry, and infrared spectroscopy to the quantification of surface functional groups on single-walled carbon nanotubes. A high-purity single-walled carbon nanotube sample was subjected to a rapid functionalization reaction that attached butyric acid moieties to the nanotube sidewalls. This sample was then subjected to thermal analysis under inert desorption conditions. Resultant infrared and mass spectrometric data were easily utilized to identify the desorption of the butyric acid groups across a narrow temperature range and we were able to calculate the degree of substitution of the attached acid groups within the nanotube backbone as 1.7 carbon atoms per hundred, in very good agreement with independent analytical measurements made by inductively coupled plasma optical emission spectrometry (ICP-OES). The thermal analysis technique was also able to discern the presence of secondary functional moieties on the nanotube samples that were not accessible by ICP-OES. This work demonstrates the potential of this technique for assessing the presence of multiple and diverse functional addends on the nanotube sidewalls, beyond just the principal groups targeted by the specific functionalization reaction. Figure3D contour map of the FTIR spectra of the species desorbed from the GAP-functionalized SWCNT sample as a function of temperature.

Reactive fillers based on SWCNTs functionalized with matrix-based moieties for the production of epoxy composites with superior and tunable properties

Composite materials based on epoxy matrix and single-walled carbon nanotubes (SWCNTs) are able to exhibit outstanding improvements in physical properties when using a tailored covalent functionalization with matrix-based moieties containing terminal amines or epoxide rings. The proper choice of grafted moiety and integration protocol makes it feasible to tune the composite physical properties. At 0.5 wt% SWCNT loading, these composites exhibit up to 65% improvement in storage modulus, 91% improvement in tensile strength, and 65% improvement in toughness. A 15 °C increase in the glass transition temperature relative to the parent matrix was also achieved. This suggests that a highly improved interfacial bonding between matrix and filler, coupled to improved dispersion, are achieved. The degradation temperatures show an upshift in the range of 40-60 °C, which indicates superior thermal performance. Electrical conductivity ranges from ~10(-13) to ~10(-3) S cm(-1), which also shows the possibility of tuning the insulating or conductive behaviour of the composites. The chemical affinity of the functionalization moieties with the matrix and the unchanged molecular structure at the SWCNT/matrix interface are responsible for such improvements.

About the solubility of reduced SWCNT in DMSO

Single-walled carbon nanotubes (SWCNT) have been reduced with sodium naphthalide in THF. The reduced SWCNT are not only soluble in dimethylsulfoxide (DMSO) to form a stable solution/suspension, but also react spontaneously at room temperature with DMSO to evolve hydrocarbon gases and are converted into functionalized SWCNT. The degree of functionalization is about 2C% and the addends are mainly methyl and small oxygen-containing hydrocarbons. The functionalized SWCNT are apparently more soluble and stable in DMSO solution. It may open a new era for further processing and applications.

Polymer nanocomposites from free-standing, macroscopic boron nitride nanotube assemblies†

Here we report the fabrication of free-standing boron nitride nanotube (BNNT) sheets by direct deposition and by vacuum filtration methods, including novel hybrid assemblies with BNNT and carbon nanotubes. Such sheets have enabled production of polymer nanocomposites with high nanotube content. Two example cases, BNNT–epoxy nanocomposites (>30 wt% BNNTs) produced by impregnation of dry sheets and BNNT sheets modified by integration of a thermoplastic polyurethane are described. Related methods have proven advantageous for carbon nanotube composites and, enabled by new technology for large scale BNNT production, such composites have now been realized with BNNTs. This represents an important milestone towards the development of BNNT-based multifunctional composites.

Single-walled carbon nanotube–modified epoxy thin films for continuous crack monitoring of metallic structures

Cracks are one of the primary forms of damage that can lead to the catastrophic failure of metallic structures. This study focuses on the application of epoxy nanocomposite thin film sensors for continuous monitoring of crack evolution in metallic structures. The core approach was to monitor the current (or resistance) change in these nanocomposite films, as cracks develop and propagate in the metallic host structure. Based on optical, electrical, and mechanical properties of epoxy resins modified with different contents of single-walled carbon nanotubes, two different nanocomposites (with 0.3 and 1.0 wt%) were chosen for the development of a crack sensor. The performance of the nanocomposite sensors was evaluated under tension–tension fatigue tests, on aluminum coupons with centrally located through thickness electrical discharge machining notches. Crack growth in the aluminum was found to transfer to the nanocomposite films in a stable mode. Once the crack was established, a linear correlation was found between the measured current and crack length with a slope of −10−11 and −10−8 A/mm for 0.3 and 1.0 wt% nanocomposites, respectively. Contact between the asperities formed on the crack surfaces in the nanocomposite film while the crack was closed at small loads (<30% of maximum load) was found to be an important limiting factor causing a large variation in measured currents during each fatigue cycle. Hence, a normalized variable based upon current change during each cycle was defined, providing a more accurate measurement of the crack size, with a crack gauge factor of ∼0.04 mm−1. In summary, the nanocomposite thin film sensor developed in this study offers both continuous crack growth monitoring and the possibility of strain sensing. The sensor is also suitable for visual inspection of the host structure due to the transparency of the developed nanocomposite film.

Integration of Single-Walled Carbon Nanotubes into a Single Component Epoxy Resin and an Industrial Epoxy Resin System

Single-walled carbon nanotubes (SWCNT) exhibit amongst the best mechanical, thermal and electrical properties of any known material. With their very high aspect ratios, SWCNT are well-suited to making ultra-light multifunctional structural composites. In this work, covalent chemistry is used to integrate SWCNT into a single component epoxy resin (aerospace grade MY0510) as well as an industrialized epoxy resin system for sporting goods. In particular, reduced SWCNT react directly with epoxide groups to create direct connections to the resin backbone. As the reduction process naturally exfoliates the SWCNT bundles, excellent dispersion is readily obtained. Substantial mechanical property improvements of the modified resin and carbon fibre composites have been observed through well-controlled processing. Their mechanical properties, specifically impact resistance, compression after impact strength and fracture toughness of the modified resin and fibre composites are discussed.