Nanotube-polymer composites for ultrafast photonics

Polymer composites are one of the most attractive near-term means to exploit the unique properties of carbon nanotubes and graphene. This is particularly true for composites aimed at electronics and photonics, where a number of promising applications have already been demonstrated. One such example is nanotube-based saturable absorbers. These can be used as all-optical switches, optical amplifier noise suppressors, or mode-lockers to generate ultrashort laser pulses. Here, we review various aspects of fabrication, characterization, device implementation and operation of nanotube-polymer composites to be used in photonic applications. We also summarize recent results on graphene-based saturable absorbers for ultrafast lasers.

Transport properties of hot-pressed bulk carbon nanotubes compacted by spark plasma sintering

Electrical and thermal transport properties of the carbon nanotube bulk material compacted by spark plasma sintering have been investigated. The electrical conductivity of the as-prepared sample shows a lnT dependence from 4 to 50 K, after which the conductivity begins to increase approximately linearly with temperature. A magnetic field applied perpendicularly to the sample increases the electrical conductivity in the range of 0-8T at all testing temperatures, indicating that the sample possesses the two-dimensional weak localization at lower temperatures (?50 K), while behaviors like a semimetal at higher temperatures (?50 K). This material acts like a uniform compact consisting of randomly distributed two dimensional graphene layers. For the same material, the thermal conductivity is found to decrease almost linearly with decreasing temperature, similar to that of a single multi-walled carbon nanotube. Magnetic fields applied perpendicularly to the sample cause the thermal conductivity to decrease significantly, but the influence of the magnetic fields becomes weak when temperature increases.

Composites take off without a parachute

The review is devoted to the cost effectiveness of composite materials applications as compared with their high performance characteristics. The use of reinforced plastics, ceramic matrix and metal matrix composites reinforced by carbon and graphite fibers in aerospace industry is considered. Until recently, the two major drivers for the application of composites in engines have been weight reduction and performance improvement. As shown, today a major challenge to be met by the industry is cost reduction.

Electrocoating of carbon fibres:a route for interface control in carbon fibre reinforced poly methylmethacrylate?

A simple method of creating defined PMMA and poly (MMA-co-Cz) electrocoatings on carbon fibres is described. The electrodeposition of poly methylmethacrylate (PMMA) onto unsized, unmodified carbon fibres was performed by simple constant current electrolyses of methylmethacrylate (MMA) monomer in dimethylformamide (DMF) solutions and the 'pur' liquid monomer using sodium nitrate and lithium perchlorate as supporting electrolytes. The presence of polymeric coatings successfully attached to the carbon fibres was verified by scanning electron microscopy and photoelectron spectroscopy (XPS). Performing the electrolysis in dilute MMA in DMF solutions ([MMA]

Green preparation of tuneable carbon-silica composite materials from wastes

Bio-oil has successfully been utilized to prepare carbon-silica composites (CSCs) from mesoporous silicas, such as SBA-15, MCM-41, KIT-6 and MMSBA frameworks. These CSCs comprise a thin film of carbon dispersed over the silica matrix and exhibit porosity similar to the parent silica. The surface properties of the resulting materials can be simply tuned by the variation of preparation temperatures leading to a continuum of functionalities ranging from polar hydroxyl rich surfaces to carbonaceous aromatic surfaces, as reflected in solid state NMR, XPS and DRIFT analysis. N2 porosimetry, TEM and SEM images demonstrate that the composites still possess similar ordered mesostructures to the parent silica sample. The modification mechanism is also proposed: silica samples are impregnated with bio-oils (generated from the pyrolysis of waste paper) until the pores are filled, followed by the carbonization at a series of temperatures. Increasing temperature leads to the formation of a carbonaceous layer over the silica surface. The complex mixture of compounds within the bio-oil (including those molecules containing alcohols, aliphatics, carbonyls and aromatics) gives rise to the functionality of the CSCs.

Functional carbon nanotubes for photonic applications

Carbon nanomaterials are an active frontier of research in current nanotechnology. Single wall Carbon Nanotube (SWNT) is a unique material which has already found several applications in photonics, electronics, sensors and drug delivery. This thesis presents a summary of the author’s research on functionalisation of SWNTs, a study of their optical properties, and potential for an application in laser physics. The first significant result is a breakthrough in controlling the size of SWNT bundles by varying the salt concentrations in N-methyl 2-pyrrolidone (NMP) through a salting out effect. The addition of Sodium iodide leads to self-assembly of CNTs into recognizable bundles. Furthermore, a stable dispersion can be made via addition polyvinylpyrrolidone (PVP) polymer to SWNTs-NMP dispersion, which indicates a promising direction for SWNT bundle engineering in organic solvents. The second set of experiments are concerned with enhancement of photoluminescence (PL), through the formation of novel macromolecular complexes of SWNTs with polymethine dyes with emission from enhanced nanotubes in the range of dye excitation. The effect appears to originate from exciton energy transfer within the solution. Thirdly, SWNT base-saturable absorbers (SA) were developed and applied to mode locking of fibre lasers. SWNT-based SAs were applied in both composite and liquid dispersion forms and achieved stable ultrashort generation at 1000nm, 1550nm, and 1800 nm for Ytterbium, Erbium and Thulium-doped fibre laser respectively. The work presented here demonstrates several innovative approaches for development of rapid functionalised SWNT-based dispersions and composites with potential for application in various photonic devices at low cost.

Supercritical carbonation of calcareous composites:influence of curing

This paper reports the effect of curing on the susceptibility of cementitious composites to carbonation using supercritical carbon dioxide. Samples made using a compression moulding technique were cured in water before and/or after carbonation and the effect on porosity, microstructure, solid phase assemblage and flexural strength was determined. In terms of development of mechanical strength, no benefit was gained from any period of pre- or post-carbonation curing regime. Yet samples cured prior to carbonation underwent minimal chemical reaction between supercritical carbon dioxide and calcium hydroxide, unhydrated cement or C-S-H. Thus there was no correlation between chemical degree of reaction and strength development. The effects responsible for the marked strength gain in supercritically carbonated samples must involve subtle changes in the microstructure of the C-S-H gel, not simple pore filling by calcium carbonate as is often postulated. © 2013 Elsevier Ltd. All rights reserved.\.

Recovery of glass fibre and carbon fibres from reinforced thermosets by batch pyrolysis and investigation of fibre re-using as reinforcement in LDPE matrix

A semi-batch pyrolysis process was used to recover samples carbon fibre and glass fibre from their respective wastes. The mechanical properties of the recovered fibres were tested and compared to those of virgin fibres, showing good retention of the fibre properties. The recovered fibres were then used to prepare new LDPE composite materials with commercial and laboratory-synthesized compatibilizers. Mild oxidation of the post-pyrolysis recovered fibres and the use of different compatibilizers gave significant improvements in the mechanical properties of the LDPE composites; however some of the manufactured composites made from recovered fibres had properties similar to those made from virgin fibres.

Facile synthesis and proposed mechanism of α,ω‐oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane) by an SN2(i) nitrato displacement method in basic media

The synthesis of a novel heterocyclic–telechelic polymer, α,ω-oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane), is described. Infrared spectroscopy (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy have been used to confirm the successful synthesis, demonstrating the presence of the telechelic-oxetanyl moieties. Synthesis of the terminal functionalities has been achieved via displacement of nitrato groups, in a manner similar to that employed with other leaving groups such as azido, bromo, and nitro, initiated by nucleophiles. In the present case, displacement occurs on the ends of a nitrato-functionalized polymer driven by the formation of sodium nitrate, which is supported by the polar aprotic solvent N,N-dimethyl formamide. The formation of an alkoxide at the polymer chain ends is favored and allows internal back-biting to the nearest carbon bearing the nitrato group, intrinsically in an SN2(i) reaction, leading to α,ω-oxetanyl functionalization. The telechelic-oxetanyl moieties have the potential to be cross-linked by chemical (e.g., acidic) or radiative (e.g., ultraviolet) curing methods without the use of high temperatures, usually below 100°C. This type of material was designed for future use as a contraband simulant, whereby it would form the predominant constituent of elastomeric composites comprising rubbery polymer with small quantities of solids, typically crystals of contraband substances, such as explosives or narcotics. This method also provides an alternative approach to ring closure and synthesis of heterocycles.

Pore confinement effects and stabilization of carbon nitride oligomers in macroporous silica for photocatalytic hydrogen production

An ordered macroporous host (mac-SiO2) has been used to prevent aggregation of layered photocatalysts based on carbon nitride. Using typical carbon nitride synthesis conditions, cyanamide was condensed at 550 °C in the presence and absence of mac-SiO2. Condensation in the absence of mac-SiO2 results in materials with structural characteristics consistent with the carbon nitride, melon, accompanied by ca. 2 wt% carbonization. For mac-SiO2 supported materials, condensation occurs with greater carbonization (ca. 6 wt%). On addition of 3 wt% Pt cocatalyst photocatalytic hydrogen production under visible light is found to be up to 10 times greater for the supported composites. Time-resolved photoluminescence spectroscopy shows that excited state relaxation is more rapid for the mac-SiO2 supported materials suggesting faster electron-hole recombination and that supported carbon nitride does not exhibit improved charge separation. CO2 temperature programmed desorption indicates that enhanced photoactivity of supported carbon nitride is attributable to an increased surface area compared to bulk carbon nitride and an increase in the concentration of weakly basic catalytic sites, consistent with carbon nitride oligomers.

Passive mode locking in erbium-doped fibre laser by carbon nanotubes

Passively mode locked fibre lasers have a variety of applications ranging from telecommunication to medical photonics. Carbon nanotubes (CNTs) have attracted recently a great deal of attention as a promising solution for saturable absorber elements required for laser mode locking (see e.g. [1-3] and references therein). CNTs can be used as a saturable absorber in passively mode locked fibre laser directly [1,2] or as a CNTs polymer composites [3]. An attractive feature of CNT-based solutions in fibre lasers is a possibility to maintain the compactness, robustness of all-fibre format and low cost through using all standard telecom compatible components. The two important technical challenges in such type of lasers are: (i) to achieve stable polarization properties of the generated radiation without using complex control elements, and, (ii) to avoid low frequency instabilities of the mode-locked pulse train. In this paper we report results of the experiments on mode-locked soliton fibre laser using the following standard components: 1m of highly doped erbium fibre (Liekki Er80-8/125) serves as the gain medium with nominal absorption of 80 dB/m at 1530 nm; a 976 nm laser diode providing up to 310mW power is used to pump the laser via a 980/1550 wavelength division multiplexing; an isolator is employed to ensure single direction oscillation; SMF-28 is used to create necessary amount of anomalous dispersion to form soliton pulse making the total cavity length around 7.83 m; the CNT-polyvinyl alcohol polymer saturable absorber sandwiched in the FC/PC connector is used as a mode-locker device (see [3] for details). © 2011 IEEE.

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.^

Quantitative and Qualitative Aspects of Dissolved Organic Carbon Leached from Senescent Plants in an Oligotrophic Wetland

We conducted a series of experiments whereby dissolved organic matter (DOM) was leached from various wetland and estuarine plants, namely sawgrass (Cladium jamaicense), spikerush (Eleocharis cellulosa), red mangrove (Rhizophora mangle), cattail (Typha domingensis), periphyton (dry and wet mat), and a seagrass (turtle grass; Thalassia testudinum). All are abundant in the Florida Coastal Everglades (FCE) except for cattail, but this species has a potential to proliferate in this environment. Senescent plant samples were immersed into ultrapure water with and without addition of 0.1% NaN3 (w/ and w/o NaN3, respectively) for 36 days. We replaced the water every 3 days. The amount of dissolved organic carbon (DOC), sugars, and phenols in the leachates were analyzed. The contribution of plant leachates to the ultrafiltered high molecular weight fraction of DOM (>1 kDa; UDOM) in natural waters in the FCE was also investigated. UDOM in plant leachates was obtained by tangential flow ultrafiltration and its carbon and phenolic compound compositions were analyzed using solid state 13C cross-polarization magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectroscopy and thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH thermochemolysis), respectively. The maximum yield of DOC leached from plants over the 36-day incubations ranged from 13.0 to 55.2 g C kg−1 dry weight. This amount was lower in w/o NaN3 treatments (more DOC was consumed by microbes than produced) except for periphyton. During the first 2 weeks of the 5 week incubation period, 60–85% of the total amount of DOC was leached, and exponential decay models fit the leaching rates except for periphyton w/o NaN3. Leached DOC (w/ NaN3) contained different concentrations of sugars and phenols depending on the plant types (1.09–7.22 and 0.38–12.4 g C kg−1 dry weight, respectively), and those biomolecules comprised 8–34% and 4–28% of the total DOC, respectively. This result shows that polyphenols that readily leach from senescent plants can be an important source of chromophoric DOM (CDOM) in wetland environments. The O-alkyl C was found to be the major C form (55±9%) of UDOM in plant leachates as determined by 13C CPMAS NMR. The relative abundance of alkyl C and carbonyl C was consistently lower in plant-leached UDOM than that in natural water UDOM in the FCE, which suggests that these constituents increase in relative abundance during diagenetic processing. TMAH thermochemolysis analysis revealed that the phenolic composition was different among the UDOM leached from different plants, and was expected to serve as a source indicator of UDOM in natural water. Polyphenols are, however, very reactive and photosensitive in aquatic environments, and thus may loose their plant-specific molecular characteristics shortly. Our study suggests that variations in vegetative cover across a wetland landscape will affect the quantity and quality of DOM leached into the water, and such differences in DOM characteristics may affect other biogeochemical processes.

Assessment of silicone polymer composites for the trace extraction of herbicides : a tool for environmental forensics

Passive samplers are not only a versatile tool to integrate environmental concentrations of pollutants, but also to avoid the use of live sentinel organisms for environmental monitoring. This study introduced the use of magnetic silicone polymer composites (Fe-PDMS) as passive sampling media to pre-concentrate a wide range of analytes from environmental settings. The composite samplers were assessed for their accumulation properties by performing lab experiments with two model herbicides (Atrazine and Irgarol 1051) and evaluated for their uptake properties from environmental settings (waters and sediments). The Fe-PDMS composites showed good accumulation of herbicides and pesticides from both freshwater and saltwater settings and the accumulation mechanism was positively correlated with the log Kow value of individual analytes. Results from the studies show that these composites could be easily used for a wide number of applications such as monitoring, cleanup, and/or bioaccumulation modeling, and as a non-intrusive and nondestructive monitoring tool for environmental forensic purposes.

Synthesis of copper carbon nanotube composite and its electrical conductivity measurement

The matrices in which Multi Walled Carbon Nanotubes (MWCNTs) are incorporated to produce composites with improved electrical properties can be polymer, metal or metal oxide. Most composites containing CNTs are polymer based because of its flexibility in fabrication. Very few investigations have been focused on CNT-metal composites due to fabrication difficulties, such as achievement of homogeneous distribution of MWCNTs and poor interfacial bonding between MWCNTs and the metal matrix. In an effort to overcome poor interfacial bonding for the Cu - MWCNT composite, silver (Ag) and nickel (Ni) resinates have been incorporated in the ball milling stage. Composites of MWCNT (16, 12, and 8 Vol %) - Cu+Ag+Ni were pelleted at 20,000 psi (669.4 Mpa) and sintered at 950 °C. The electrical conductivity results measured by four probe meter showed that the conductivity decreases with increase in the porosity. Moreover from these results it can also be stated that an addition of optimum value of (12 Vol %) MWCNT leads to high electrical conductivity (9.26E+07 s-m"), which is 50% greater than the conductivity of Cu. It is anticipated that the conductivity can be increased substantially with hot isostatic pressing of the pellet.