Kerf Taper Defect Minimization Based on Abrasive Waterjet Machining of Low Thickness Thermoplastic Carbon Fiber Composites C/TPU.

Carbon fiber-reinforced thermoplastics (CFRTPs) are materials of great interest in industry. Like thermosets composite materials, they have an excellent weight/mechanical properties ratio and a high degree of automation in their manufacture and recyclability. However, these materials present difficulties in their machining due to their nature. Their anisotropy, together with their low glass transition temperature, can produce important defects in their machining. A process able to machine these materials correctly by producing very small thermal defects is abrasive waterjet machining. However, the dispersion of the waterjet produces a reduction in kinetic energy, which decreases its cutting capacity. This results in an inherent defect called a kerf taper. Also, machining these materials with reduced thicknesses can increase this defect due to the formation of a damage zone at the beginning of cut due to the abrasive particles. This paper studies the influence of cutting parameters on the kerf taper generated during waterjet machining of a thin-walled thermoplastic composite material (carbon/polyurethane, C/TPU). This influence was studied by means of an ANOVA statistical analysis, and a mathematical model was obtained by means of a response surface methodology (RSM). Kerf taper defect was evaluated using a new image processing methodology, where the initial and final damage zone was separated from the kerf taper defect. Finally, a combination of a hydraulic pressure of 3400 bar with a feed rate of 100 mm/min and an abrasive mass flow of 170 g/min produces the minimum kerf taper angle.

Different Methods of Dispersing Carbon Nanotubes in Epoxy Resin and Initial Evaluation of the Obtained Nanocomposite as a Matrix of Carbon Fiber Reinforced Laminate in Terms of Vibroacoustic Performance and Flammability.

Different industrial mixing methods and some of their combinations ((1) ultrasound; (2) mechanical stirring; (3) by roller machine; (4) by gears machine; and (5) ultrasound radiation + high stirring) were investigated for incorporating multi-walled carbon nanotubes (MWCNT) into a resin based on an aeronautical epoxy precursor cured with diaminodiphenylsulfone (DDS). The effect of different parameters, ultrasound intensity, number of cycles, type of blade, and gear speed on the nanofiller dispersion were analyzed. The inclusion of the nanofiller in the resin causes a drastic increase in the viscosity, preventing the homogenization of the resin and a drastic increase in temperature in the zones closest to the ultrasound probe. To face these challenges, the application of high-speed agitation simultaneously with the application of ultrasonic radiation was applied. This allowed, on the one hand, a homogeneous dispersion, and on the other hand, an improvement of the dissipation of heat generated by ultrasonic radiation. The most efficient method was a combination of ultrasound radiation assisted by a high stirring method with the calendar, which was used for the preparation of a carbon fiber reinforced panel (CFRP). The manufactured panel was subjected to dynamic and vibroacoustic tests in order to characterize structural damping and sound transmission loss properties. Under both points of view, the new formulation demonstrated an improved efficiency with reference to a standard CFRP equivalent panel. In fact, for this panel, the estimated damping value was well above the average of the typical values representative of the carbon fiber laminates (generally less than 1%), and also a good vibroacoustic performance was detected as the nanotube based panel exhibited a higher sound transmission loss (STL) at low frequencies, in correspondence with the normal mode participation region. The manufactured panel was also characterized in terms of fire performance using a cone calorimeter and the results were compared to those obtained using a commercially available monocomponent RTM6 (Hexcel composites) epoxy aeronautic resin with the same process and the same fabric and lamination. Compared to the traditional RTM6 resin, the panel with the epoxy nanofilled resin exhibits a significant improvement in fire resistance properties both in terms of a delay in the ignition time and in terms of an increase in the thermal resistance of the material. Compared to the traditional panel, made in the same conditions as the RTM6 resin, the time of ignition of the nanotube-based panel increased by 31 seconds while for the same panel, the heat release rate at peak, the average heat release rate, and the total heat release decreased by 21.4%, 48.5%, and 15%, respectively. The improvement of the fire performance was attributed to the formation of a non-intumescent char due to the simultaneous presence of GPOSS and carbon nanotubes.

Microextraction by packed sorbents combined with surface-enhanced Raman spectroscopy for determination of musk ketone in river water.

Microextraction by packed sorbents (MEPS) combined with Surface-enhanced Raman spectroscopy (SERS) was investigated, and applied to the determination of musk ketone (MK) in river water samples. The full MEPS-SERS method includes analyte enrichment by MEPS preconcentration with C18 sorbent followed by SERS detection supported by silver nanoparticles. An eluent drop containing the analyte is deposited directly from the MEPS syringe on a CaF2 glass plate. When the drop has dried, a specific volume of silver nanoparticles solution is added on it before each SERS measurement. Several experimental variables were studied in depth; under the optimum experimental conditions MK can be extracted from a 500 µL sample with recoveries in the range 47-63 %. The limit of detection was 0.02 mg L(-1) and the relative standard deviation 15.2 % (n = 4). Although not investigated in this work, the proposed method might be suitable for in-situ monitoring, because of the portability of the Raman spectrometer used.

Determination of TNT explosive based on its selectively interaction with creatinine-capped CdSe/ZnS quantum dots.

Here, a creatinine-modified CdSe/ZnS quantum dots fluorescent probe has been prepared and used for sensing 2,4,6,-trinitrotoluene explosive (TNT). The proposed method is based on the selective interaction between creatinine and nitroaromatic compounds according to the well-known Jaffé reaction. The procedure for the synthesis of creatinine-CdSe/ZnS reagent is very simple and reproducible and its fluorescent characteristics are reported. We found that the presence of TNT quenches the original fluorescence of creatinine-QD according to the Stern-Volmer model. Under the working conditions, the calibration plot of Io/I versus concentration of TNT was linear in the range 10-300µg L(-1) (R(2)=0.996). The mechanism interaction is discussed. The selectivity of fluorescence quenching of creatinine-QD for TNT has been evaluated. Finally, the potential application of the proposed methodology for the determination of TNT in spiked soils is demonstrated. For the analysis of soil samples a solid-liquid extraction is carried out and a four-point standard addition protocol is used to correct the matrix effect. The method, which is simple and rapid, allows the detection of 0.057µg g(-1) of TNT in soil samples. This sensor could be a useful tool for environmental studies, a crucial topic for nanotechnology nowadays.

Liquid-liquid extraction assisted by a carbon nanoparticles interface. Electrophoretic determination of atrazine in environmental samples.

A novel method for the determination of atrazine, using liquid-liquid extraction assisted by a nanoparticles film formed in situ and composed of organic solvent stabilized-carbon nanoparticles, is described. The presence of nanoparticles located at the liquid-liquid interface reinforced the extraction of analyte from matrix prior to capillary electrophoresis (CE) analysis. Some influential experimental variables were optimized in order to enhance the extraction efficiency. The developed procedure confirmed that carbon nanoparticles, especially multi-walled carbon nanotubes, are suitable to be used in sample treatment processes introducing new mechanisms of interaction with the analyte. The application of the proposed preconcentration method followed by CE detection enabled the determination of atrazine in spiked river water providing acceptable RSD values (11.6%) and good recoveries (about 87.0-92.0%). Additionally, a similar extraction scheme was tested in soil matrices with a view to further applications in real soil samples.

Graphene nanoparticles as pseudostationary phase for the electrokinetic separation of nonsteroidal anti-inflammatory drugs.

The exceptional properties of graphene (G) were exploited here to facilitate capillary electrokinetic separations. Two types of commercially available G consisting of nanoparticles containing-one to three and-four to six G sheets, respectively, were compared for this purpose. Both proved effective in separating the arylpropyl derivatives of nonsteroidal anti-inflammatory drugs. The highest resolution and shortest migration times were obtained with G containing high amount of single and double G nanosheets. G affords higher resolution than other types of nanoparticles; stable suspensions can be easily prepared and used as BGE without the need of adding an additional surfactant. This results in a high reproducibility in migration times and stability in background noise. The LOD and LOQ obtained by using G nanoparticles as pseudostationary phases spanned the range 0.29-1.18 mg/L and 0.95-3.95 mg/L, respectively, and the RSD was less than 4.7% in all instances.

Ionic liquid combined with carbon nanotubes: a soft material for the preconcentration of PAHs.

The combination of ionic liquids with carbon nanotubes has opened a new possibility of ionic liquids as modifiers for carbon nanotubes. Upon being ground into ionic liquids, carbon nanotube bundles are untangled, and the resultant fine bundles form a network structure. This is due to the possible specific interaction between the imidazolium ion component and the p-electronic nanotube surface. The resultant soft material has a high capacity to adsorb/absorb analytes from samples. In this work, the soft material was prepared by mixing 15 mg of carbon nanotubes with 300 µL of IL. The soft material was immobilized on cotton fibers to perform the preconcentration of aromatic compounds such as PAHs from river water samples. The most important fact is the synergic effect between the ionic liquid and the carbon nanotubes which results in a high capacity to preconcentrate analytes. In fact, the sorption capacity of 15 mg of the soft material containing 0.55 mg of MWNT and 11 µl of IL is two times higher than the capacity of 15 mg of MWNT and 3.7 times higher than that of 100 µl IL.

Solid-phase extraction of nitrophenols in water by using a combination of carbon nanotubes with an ionic liquid coupled in-line to CE.

This paper describes the combined use of carbon nanotubes and an ionic liquid directly coupled in-line to commercial CE equipment for sample treatment. The extraction unit operates as a spin column to preconcentrate the analytes. The extraction unit is inserted into the sample vial. The elution is performed in-line, placing the vial on the carrousel of the CE equipment. The joint use of carbon nanotubes and ionic liquids as sorbent is based on the high adsorption capacity of these materials, which makes them highly suitable for microextraction purposes. The LOQ of analytes were within the range of 0.65-0.83 µg/L with a RSD of less than 7%. The values of recovery range between 90 and 112%. The absolute recovery obtained from samples containing 1 µg/L of analytes was 38%.

Determination of pesticides by capillary chromatography and SERS detection using a novel Silver-Quantum dots "sponge" nanocomposite.

In this work the at-line capillary-liquid chromatography-(microdispenser)-surface-enhanced Raman spectroscopy coupling was investigated and applied to the determination of pesticides. The use of a microdispenser combined with the use of a precise and reproducible surface enhanced Raman spectroscopy (SERS) substrate yielded a chromatographic detection system with excellent analytical properties. The microdispenser was coupled to a moving CaF2 hot (80 °C) plate using a flow-through microdispenser interface to collect the microdrops. Ag-QD nanocomposites, which are highly reproducible thanks to their sponge-shaped structure, were used as substrate with which to measure the SERS spectra in each spot of the plate. The limits of detection ranged from 0.2 to 0.5 ng of pesticide injected (chlortoluron, atrazine, diuron and terbuthylazine) and the precision ranged between 10.2 and 12.5%.

(CdSe/ZnS QDs)-ionic liquid-based headspace single drop microextraction for the fluorimetric determination of trimethylamine in fish.

Here, we propose the use of ionic liquid-modified QDs for the combination of ionic liquid-based headspace single drop microextraction technique (IL-HS-SDME) and QD-based fluorimetric detection. In that way, we exploit the advantages of ILs as extractant solvent and the use of QDs as fluorescence detection probe. After in situ generation of volatile trimethylamine (TMA) from fish samples, the analyte was extracted and preconcentrated directly onto a (QD)IL microdrop by HS-SDME. Then, TMA was quantified through the enhancing effect produced on the initial fluorescence of the (QD)IL dispersion. The working conditions for the (QD)IL-HS-SDME procedure were: 20 µL microdrop of (QD)IL exposed for 2 min to the headspace of a 5 mL aqueous sample (0.2 g of fish in 10 M NaOH) placed in a 10 mL vial with stirring and thermostatted at 50-60 °C. For the detection, the microdrop was transferred to a microcuvette with 300 µL of acetonitrile and the fluorescence was recorded (λ(em) = 570 nm, λ(exc) = 400 nm). Under the selected conditions, the analytical response was linear over the range from 0.05 to 0.25 mg L(-1) (R(2) = 0.997) with a detection limit of 0.014 mg L(-1) (0.35 µg TMA per gram of fish) and the relative standard deviation was 3.5% (n = 5). The proposed method was applied to the determination of TMA in hake fish samples with satisfactory results.

Determination of nanoparticles in biological matrices.

Human exposure to nanoparticles has increased considerably due to anthropogenic activities dominated by coal and diesel oil fuel combustion. Not only the inhalation of nanoparticles, which nowadays is considered to be the most significant via of exposure to nanomaterials, but also the gradually more employment of nanoparticles in products such as cosmetics, deodorants, textiles, or even food is broadening the exposure to those materials. Developing the previous applications will obviously require the use of analytical methodologies to analyse biological matrices in order to assess potential risks in their use and take appropriate corrective actions. This chapter describes a general overview of the most important analytical techniques for the analysis of nanoparticles in biological matrices.

Determination of pyrimidine and purine bases by reversed-phase capillary liquid chromatography with at-line surface-enhanced Raman spectroscopic detection employing a novel SERS substrate based on ZnS/CdSe silver-quantum dots.

We have developed a new SERS substrate based on the reduction of silver nitrate in the presence of ZnS-capped CdSe quantum dots. This substrate showed higher sensitivities as compared to a hydroxylamine-reduced silver sol. On the basis of this new substrate, at-line SERS detection was coupled with capillary liquid chromatography (cap-LC) for the separation and selective determination of pyrimidine and purine bases. For this purpose, wells of a dedicated microtiter plate were loaded with 20 µL of the SERS substrate and placed on an automated x,y translation stage. A flow-through microdispenser capable of ejecting 50 pL droplets, at a frequency 100 Hz, was used as the interface to connect the cap-LC system to the wells loaded with SERS substrate. A detailed study of the dependence of both the separation and the surface-enhanced Raman spectra of each base on the pH was performed to optimize the system for maximum sensitivity and selectivity. Highly satisfactory analytical figures of merit were obtained for the six investigated bases (cytosine, xanthine, hypoxanthine, guanine, thymine, and adenine) with detection limits ranging between 0.2 and 0.3 ng injected on the capillary LC column, and the precisions were in the range of 3.0-6.3%.

Determination of amines based on their interaction with QDs: effect of the formation QD-assemblies.

Assemblies of closed nanoparticles have focused interest because they exhibit new optical and chemical properties. The use of a 1D covalent strategy for quantum dots-assemblies has been proposed in this work as novelty. It was studied the effect of use different dithiols, including aromatic and aliphatic dithiol compounds, on the formation of QDs-assemblies in order to establish the influence of the linker's structure on the geometry of the assemblies, and hence on their properties. As a second part of the work, the changes on analytical response to analytes thanks to the formation of QDs-assemblies when dithiols are added were studied for firs time. For this study, some biogenic amines were selected as target analytes. We observed an improvement of 2.7-4 times in the sensitivity, expressed as slope of the calibration graph, when the dithiols were added to the system obtaining QDs-assemblies.

Calix[8]arene coated CdSe/ZnS quantum dots as C60-nanosensor.

Here, we report an optical sensor for fullerene C(60) in water using CdSe/ZnS quantum dots coated by p-tertbutylcalix[8]arene. This C(60)-nanosensor is based on the selective host-guest interaction between fullerene C(60) and p-tertbutylcalix[8]arene. The procedure for the synthesis of p-tertbutylcalix[8]arene-CdSe/ZnS complex is described, and its fluorescent characteristics are also reported. We found that the interaction between C(60) fullerene and p-tertbutylcalix[8]arene-CdSe/ZnS complex quenches the original fluorescence of calix-QDs according to the Stern-Volmer equation. The mechanism of interaction is discussed. Finally, the potential application of the proposed method using the designed nanosensor for determination of C(60) in spiked environmental river water samples is demonstrated. For the analysis of river samples, a liquid-liquid extraction multistep preconcentration procedure is proposed. The method, which is simple and rapid, allows the detection of 5 µg L(-1) of fullerene. This sensor could be a useful tool for environmental and toxicological studies.

Colistin-functionalised CdSe/ZnS quantum dots as fluorescent probe for the rapid detection of Escherichia coli.

Intensely fluorescent, colistin-functionalised CdSe/ZnS QDs (Colis-QDs) nanoparticles, are synthesized and used as sensitive probes for the detection of Escherichia coli, a Gram-negative bacteria. Colistin molecules are attached to the terminal carboxyl of the mercaptoacetic acid-capped QDs in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) as amide bond promoters. The TEM analysis of bacteria treated with Colis-QDs conjugates showed the accumulation of Colis-QDs in the cell wall of E. coli. Under the recommended working conditions, the method provides a detection limit as few as 28 E. coli cells per mL, which is competitive which more elaborate detection systems. The simplicity of the method together with short analysis time (< 15 min, without including preparation and photoactivation of the Colis-QDs conjugate) make the proposed approach useful as quick bacteria screening system.

Rapid fluorescence determination of diquat herbicide in food grains using quantum dots as new reducing agent.

CdSe/ZnS QDs have demonstrated capacity to act as reducing agent in organic media such as acetonitrile and ethanol. By using fluorescence and Raman spectroscopy, it has been demonstrated that QDs reduce diquat herbicide to its monocation radical. The reaction is characterized to present a high reaction rate making possible to perform the reaction by simple filtration of the solution containing the herbicide through a QDs modified filter. The monocation radical presents a high fluorescence emission spectrum which was selected as the analytical signal to quantify the diquat herbicide. The method described here for the analysis of diquat herbicide in oat grains is simple and fast allowing the analysis of trace level of herbicide in only 6 min. The excellent sensitivity and reproducibility of the methods indicate that the reaction is favoured from both thermodynamic and kinetic point of view. The results presented open up the possibility to use QDs as redox agent. The sensitivity of the method expressed as detection limit was only of 0.01 mg kg(-1).The lineal range was between 0.05 and 0.5 mg kg(-1). The time of analysis per sample, including extraction, reaction and fluorescent measurement was only of 6 min.

Capillary electrophoresis method for the characterization and separation of CdSe quantum dots.

This paper presents a simple and rapid methodology to separate and characterize free CdSe quantum dots (QDs) in aqueous medium by capillary electrophoresis (CE). First, we describe a controlled derivatization procedure to obtain water-soluble QDs through noncovalent interactions. This derivatization methodology was based on the formation of a complex between the QDs and several types of surfactants to enhance the hydrophilicity and stability of the CdSe QDs. The surfactants used to achieve the surface functionalization were trioctylphosphine oxide/trioctylphosphine (TOPO/TOP) and sodium dodecyl sulfate (SDS). Different CdSe QDs core sizes were synthesized as function of the nanocrystals growing time and then subjected to controlled coating. These free QDs were separated by capillary zone electrophoresis (CZE) based on the differences in the charge-to-mass ratio of the QDs-TOPO/TOP-SDS complexes, and the detection was carried out with UV-vis and laser-induced fluorescence (LIF) techniques obtaining detection limits 5 times lower with CE-LIF. Under the optimal working conditions, four different-sized QDs were successfully separated whose average sizes were 3.1, 3.6, 4.3, and 4.9 nm, and the size distribution was less than 7% for all of them [calculated from the full width at half-maximum (fwhm) of the fluorescence spectra and confirmed by high-resolution transmission electron microscopy (HTEM)]. Therefore, we were able to separate QDs that differ in only 0.5 nm in diameter and 19 nm in fluorescence emission maximum. This corresponds to the better resolution achieved in the analysis of these kinds of nanoparticles. Finally, a correlation between the migration times plus or minus peak width and the core sizes plus or minus size distribution was established.

In situ synthesis of magnetic multiwalled carbon nanotube composites for the clean-up of (fluoro)quinolones from human plasma prior to ultrahigh pressure liquid chromatography analysis.

Magnetic nanoparticles (MNPs) were deposited onto multiwalled carbon nanotubes (MWCNTs) by in situ high-temperature decomposition of the magnetic precursor [iron(III)] and MWCNTs, in ethylene glycol. This one-step synthetic method was applied to commercially available carbon nanotubes (CNTs). Scanning electron micrographs of the resulting products revealed that MNPs decorated the surface of the MWCNTs. The hybrid nanoparticles thus obtained were used for sampling and cleanup in the determination of eight fluoroquinolones (FQs) and two quinolones (Qs) at trace levels by ultra performance liquid chromatography (UPLC). A systematic study of analyte adsorption and desorption was conducted with MNPs and MWCNTs separately. Although both solid phases adsorbed the analytes to some extent, the much higher recoveries were obtained by using the MNP-MWCNT composite which was thus selected to treat plasma samples containing FQs and Qs. Lower accuracies were determined at spiked plasma compared to the standard solution caused by the complexation affinity of the analytes with proteins because high recoveries were observed when deproteinization was performed before treating the sample with the magnetic MWCNTs. The performance characteristics of the optimized method were determined, and the method was applied to the analysis of plasma samples from antibiotic-treated patients. On the basis of the results, the use of an in situ synthesized MWCNT-MNP composite allows the simple, expeditious sampling and treatment of such complex biological samples for the subsequent determination of FQs and Qs present at free form.

Carbon nanotube-quantum dot nanocomposites as new fluorescence nanoparticles for the determination of trace levels of PAHs in water.

Amplification of fluorescence is a nanoscale phenomenon which is particularly pronounced in close proximity to metal nanostructures. We have demonstrated for first time that fluorescence amplification can also be produced by single-walled carbon nanotube-quantum dot nanocomposites (SWCNT-QDs). Concretely we exploit the adsorption capabilities of SWCNTs to facilitate the interaction of analytes with the nanoparticle. The fluorescence amplification mechanism is discussed in the paper. The analytical potential of these nanocomposites has been demonstrated for the detection of trace levels of polycyclic aromatic compounds (PAHs) in river water samples. Compared with QDs nanoparticles, the fluorescence enhancement achieved with the SWCNT-QDs nanocomposites was 3.6-5.5 times higher.

Quantum dots luminescence enhancement due to illumination with UV/Vis light.

Quantum dots (QDs) are a novel class of inorganic fluorophores, which are gaining widespread recognition as a result of their exceptional photophysical properties. They are rapidly being integrated into existing and emerging technologies, and could play an important role in many areas in the future. Significant phenomena, such as photoactivation, are still unknown and must be understood and more fully defined before they can be widely validated. This review provides an overview of the photoactivation process of quantum dots in a systematic way, covering QD characteristics, solubilisation strategies, and a description of different photoactivation mechanisms, depending on the type of QDs and their surrounding environment.