Fiber Coating Techniques

Roll coating is widely used for uniform, whether flat or cylindrical, surfaces including fiber bundles. In a roll coating process, fibers are coated between two rollers, an applicator roller and a backup roller coating is fed continuously to the applicator roller by a feed roller which runs partially immersed in a coating bath and the backup roller pulls the fibers by rotating in opposite directions. Slow 

Most suitable for electrically conducting materials such as carbon fibers, the electrochemical processes involve deposition of polymer coatings on the fiber surface through electrodeposition or electropolymerization techniques. The major advantage of these processes is that a uniform layer of controlled thickness and variable polymer structure and properties can be obtained by controlling the current and the solution concentration. 

The electrochemical polymerization process is achieved by polymerization of monomers in an electrolytic cell (Subramanian and Jakubowski, 1978). The electrode is the source of active species that initiates the polymerization. It is necessary to select a solvent electrolyte system which is capable of forming a solution with the monomer and having sufficient current-conducting properties. In the process employed by Bell and coworkers (Bell et al., 1987 Wimolkiatisak and 

1989 Rhee and Bell, 1991), random copolymers of methyl acrylate and acrylonitrile were directly polymerized onto the carbon fiber surface. Dimethyl formamide, dimethyl sulfoxide and distilled water proved to be useful as solvents for this process. Polymerization can take place on the carbon fiber electrode, with initial wetting of the fiber surface leading to better adhesion of the polymer formed. The structure and properties of the polymer can be varied by employing different vinyl and cyclic monomers in homopolymerization. Chemical bond can also be formed, such as polymer grafting to the carbon fiber surface. 

The condensation polymerization process, employed recently by Skourlis et al. (1993) and Duvis et al. (1993), involves immersion of carbon fibers in a solution containing hexamethylenediamine and sodium carbonate. Dried carbon fibers are then immersed in a dipolychloride solution in carbon tetrachloride where the interfacial polycondensation reaction takes place. The result is that a thin layer of polyamide (nylon 6,6) coating is deposited on the continuous carbon fiber, whose thickness is controlled though by varying the diamine concentration. 

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Solid phase micro extraction (SPME) is a techniques in which a silica fiber coated with a thin film of polymer is brought into contact with an aqueous matrix where the organics in solution partition onto the fiber. The fiber is subsequently placed into the injector of a GC where the heat causes the release of analyte onto the column. This has been applied to endosulfan (a- and (3-) and endosulfan sulfate in water with limits of detection of less than 0.3 pg/L reported (Magdic and Pawliszyn 1996). 

The development of new fiber coatings in the near future should further improve the specificity of SPME and overcome some of the observed matrix effects. Quantification by stable isotope dilution gas chromatography/mass spectrometry (GC/MS) may assist in improving analytical performance. Along with the possible application of micro LC and capillary LC columns to in-tube SPME, the development of novel derivatization methods and the potential for the analysis of fumigant pesticides, SPME appears to be a technique with a future in the analysis of pesticide residues in food. 

The contribution by Rouzaud et al. teaches to apply a modified version of high resolution Transmission Electron Microscopy (TEM) as an efficient technique of quantitative investigation of the mechanism of irreversible capacity loss in various carbon candidates for application in lithium-ion batteries. The authors introduce the Corridor model , which is interesting and is likely to stimulate active discussion within the lithium-ion battery community. Besides carbon fibers coated with polycarbon (a candidate anode material for lithium-ion technology), authors study carbon aerogels, a known material for supercapacitor application. Besides the capability to form an efficient double electric layer in these aerogels, authors... 

Sol-gel coating technique for optical chemical sensors and biosensors is now in extensive research phase. For example, the side-coating of optical fibers or waveguides in evanescent-wave sensors it is particularly important to control precisely the sensitivity determining parameters, such as the coating thickness and length45. 

A newer addition is in-tube SPME that makes use of an open capillary device and can be coupled online with GC, HPLC, or LC/MS. All these techniques and their utilization in pharmaceutical and biomedical analysis were recently reviewed by Kataoka.45 Available liquid stationary fiber coatings for SPME include polydimethylsiloxane (PDMS) and polyacrylate (PA) for extracting nonpolar and polar compounds, respectively. Also in use for semipolar compounds are the co-polymeric PDMS-DVB, Carboxen (CB)-PDMS, Carbowax (CW)-DVB, and Carbowax-templated resin (CW-TPR). A few examples of in-tube SPME extractions from biological matrices are shown in Table 1.19 and drawn from Li and coworkers.166... 

In the 1990s, Pawliszyn [3] developed a rapid, simple, and solvent-free extraction technique termed solid-phase microextraction. In this technique, a fused-silica fiber is coated with a polymer that allows for fast mass transfer—both in the adsorption and desorption of analytes. SPME coupled with GC/MS has been used to detect explosive residues in seawater and sediments from Hawaii [33]. Various fibers coated with carbowax/divinylbenzene, polydimethylsiloxane/divinylbenzene, and polyacrylate are used. The SPME devices are simply immersed into the water samples. The sediment samples are first sonicated with acetonitrile, evaporated, and reconstituted in water, and then sampled by SPME. The device is then inserted into the injection port of the GC/MS system and the analytes thermally desorbed from the fiber. Various... 

The first major obstacle encountered in developing a successful coating seems to be the method of application. The coating must wet the liber properly, be uniform in thickness and, most preferably, be free of porosity extending to the surface of the substrate. The conventional methods of applying coatings to bulk substrates arc not suitable nor adequate for fibers of small diameter. It is important to note that the selection criteria for one coating technique over another are most often diflerent. 

Arthur and Pawliszyn introduced solid-phase microextraction (SPME) in 1990 as a solvent-free sampling technique that reduces the steps of extraction, cleanup, and concentration to a unique step. SPME utilizes a small segment of fused-silica fiber coated with a polymeric phase to extract the analytes from the sample and to introduce them into a chromatographic system. Initially, SPME was used to analyze pollutants in water - via direct extraction. Subsequently, SPME was applied to more complex matrixes, such as solid samples or biological fluids. With these types of samples, direct SPME is not recommended nevertheless, the headspace mode (HSSPME) is an effective alternative to extracting volatile and semivolatile compounds from complex matrixes. (Adapted from Llompart et ah, 2001)... 

If suitable equipment for processing the polymer melt is not available, or if the polymer will not melt, or melts only with decomposition, the processing may be carried out from solution. This technique, however, is limited to the fabrication of films, membranes, fibers, coatings, and adhesives. 

Recently, Caster et al. described the surface modification of multifilament fibers such as nylon or Kevlar [70]. Coating techniques using preformed ROMP-based polymers and process contact metathesis polymerization (CMP), initially described by Grubbs et al. [71], were both used. The latter involves a procedure where the initiator is physisorbed onto the surface of a substrate and fed with a ROMP-active monomer that finally encapsulates the substrate. These modified fibers showed improved adhesion to natural rubber elastomers. 

Solid-phase microextraction (SPME). used as a sample introduction technique for high speed gc, utilizes small-diameter fused-silica fibers coated with polymeric stationary phase for sample extraction and concentration. SPME lias been utilized for determination of pollutants in aqueous solution by the adsorption of analyte onto stationary-phase coated fuscd-silica fibers, followed by thermal desorption in the injection system of a capillary gas chromatograph. Full automation can be achieved using an autosampler. 

SPME is a sample-preparation technique based on absorption that is useful for extraction and concentration of analytes either by submersion in a liquid phase or exposure to a gaseous phase (Belardi and Pawliszyn, 1989 Arthur et al., 1992). Following exposure of the fiber to the sample, absorbed analytes can be thermally desorbed in a conventional GC injection port. The fiber behaves as a liquid solvent that selectively extracts analytes, with more polar fibers having a greater affinity for polar analytes. Headspace extraction from equilibrium is based on partition coefficients of individual compounds between the food and headspace and between the headspace and the fiber coat-... 

Solid-phase microextraction uses a 1-cm length of focused silica fiber, coated on the outer surface with a stationary phase and bonded to a stainless steel plunger holder that looks like a modified microliter syringe. The fused-silica fiber can be drawn into a hollow needle by using the plunger. In the first process, the coated fiber is exposed to the sample and the target analytes are extracted from the sample matrix into the coating. The fiber is then transferred to an instrument for desorption. The technique has been promoted by Pawliszyn (69). 

Zhou S.N., X. Zhang, G. Ouyang, A. Eshaghi, and J. Pawliszyn. 2007. On-fiber standardization technique for solid-coated solid-phase microextraction. Anal. Chem. 79 1221-1230. 

Among the above-mentioned methods, SPME is relatively new. It combines sample preparation and injection of the sample into one step. Analytes are adsorbed on a polymeric fiber coated with a stationary phase such as polydimethylsiloxane, which is thermally desorbed in the injection port at 250 °C. The successful use of the technique for the GC/MS analysis of the nerve agents in water has been described (42). Levels of less than... 

Solid phase micro-extraction (SPME) allows isolation and concentration of volatile components rapidly and easily without the use of a solvent. These techniques are independent of the form of the matrix liquids, solids and gases can be sampled quite readily. SPME is an equilibrium technique and accurate quantification requires that the extraction conditions be controlled carefully. Each chemical component will behave differently depending on its polarity, volatility, organic/water partition coefficient, volume of the sample and headspace, speed of agitation, pH of the solution and temperature of the sample (Harmon, 2002). The techniques involve the use of an inert fiber coated with an absorbant, which govern its properties. Volatile components are adsorbed onto a suitable SPME fiber (which are usually discriminative for a range of volatile components), desorbed in the injection chamber and separated by a suitable GC column. To use this method effectively, it is important to be familiar with the factors that influence recovery of the volatiles (Reineccius, 2002). 

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