SFC-FTIR

Figure 9.9 Schesatic diagrans of flow-through cell. A, and solvent elimination interfar B, for SFC/FTIR. For A (1) polished stainless steel lig..v.pipe (2) zinc selenide window (3) PTFE spacer (4) viton rubber o-ring (5) graphitized Vespel nicroferrule (6) deactivated fused-silica capillary tubing (7) bolt with Allen nut (8) stainless steel end-fitting and (9) stainless steel body of flow cell.

Wieboldt et al. [560] have described SFE-SFC-FTIR analysis of hindered phenol primary antioxidants and phosphite secondary antioxidants in PE. SFE is more selective for the lower-range low-MW polymer than Soxhlet-type extraction. This yields a chromatogram with less interference from low-MW polymer peaks in the region where the additive components elute. As a result, SFE appears to be a better choice than Soxhlet-type extraction for the selective removal of additives from flaked polymer. SFE and dissolution/precipitation methods were compared for a PVC/stabiliser system [366]. 

There is a need for increased chromatography-FTIR sensitivity to extend IR analysis to trace mixture components. GC-FTIR-MS was prospected as the method of choice for volatile complex mixture analysis [167]. HPLC-FT1R, SFC-FTIR and TLC-FTIR are not as sensitive as GC-FTIR, but are more appropriate for analyses involving nonvolatile mixture components. Although GC-FTIR is one of the most developed and practised techniques which combine chromatography (GC, SFC, HPLC, SEC, TLC) and FUR, it does not find wide use for polymer/additive analysis, in contrast to HPLC-FTIR. 

Consequently, the major experimental options for the analyst are packed or capillary SFC, mobile phase with/without modifier and off-line or on-line mode, namely direct deposition (DD-SFC-FUR) vs. flowcell. Both small-bore packed columns and narrow-bore open-tubular columns have been used for SFC-FTIR analysis using a pressure-stable, thermostated, flow-cell or solvent elimination interfaces. 

Figure 7.16 Schematic representation of off-line SFC-FTIR. After deposition of the eluites on to a moving ZnSe substrate the window is moved to the focus of a stand-alone FTIR microscope, where the spectmm of each spot is measured with the plate stationary. After Griffiths et al. [374]. Reprinted from P.R. Griffiths et al., in Hyphenated Techniques in Supercritical Fluid Chromatography and Extraction (K. Jinno, ed.), pp. 83-101, Copyright (1992), with permission from Elsevier...

Table 7.34 Main characteristics of hyphenated flow-cell SFC-FTIR...

The problems discussed above may be circumvented by eliminating the mobile phase before measuring the spectra of the eluites, as first demonstrated by Shafer et al. [379] for pSFC-FTIR. Each eluite was deposited on a moving glass plate, on which a layer of powdered KC1 or KBr had been laid down from methanol slurry for diffuse reflectance spectroscopy (SFC-DRIFTS). Solvent elimination SFC-FTIR after deposition of the eluites on to a moving ZnSe substrate is quite straightforward the window is moved to the... 

Table 7.35 Main characteristics of solvent-elimination SFC-FTIR...

Infrared coupling to SFC has further developed into the use of two or more complementary detectors, such as cSFC-FTTR-MS [382] and cSFC-UV-FTIR-FID. Nevertheless, SFC-FTIR appears not to have developed the same importance as SFC-MS (cf. Section 13.2.2). 

Yang et al. [389] rapidly distinguished compounds extracted from paper, using on-line SFE-SFC-FHR in conjunction with principal component analysis. The quantitative determination of the surfactant mixture Triton X-100 and other complex oligoether surfactants by means of cSFC-FTIR flow-cells has been reported [390,391]. Practical applications of SFC-FTIR include the determination of nonvolatile compounds from microwave-susceptible packaging that may migrate into heated food. Another application is the analysis of fibre finishes on fibre/textile matrices. 

On-line SFE-pSFC-FTIR was used to identify extractable components (additives and monomers) from a variety of nylons [392]. SFE-SFC-FID with 100% C02 and methanol-modified scC02 were used to quantitate the amount of residual caprolactam in a PA6/PA6.6 copolymer. Similarly, the more permeable PS showed various additives (Irganox 1076, phosphite AO, stearic acid - ex Zn-stearate - and mineral oil as a melt flow controller) and low-MW linear and cyclic oligomers in relatively mild SCF extraction conditions [392]. Also, antioxidants in PE have been analysed by means of coupling of SFE-SFC with IR detection [121]. Yang [393] has described SFE-SFC-FTIR for the analysis of polar compounds deposited on polymeric matrices, whereas Ikushima et al. [394] monitored the extraction of higher fatty acid esters. Despite the expectations, SFE-SFC-FTIR hyphenation in on-line additive analysis of polymers has not found widespread industrial use. While applications of SFC-FTIR and SFC-MS to the analysis of additives in polymeric matrices are not abundant, these techniques find wide application in the analysis of food and natural product components [395]. 

SFC-based methods still need to show their potential, in spite of past great promise. pSFC-APCI-MS is a powerful method for identification of polymer additives, provided that a library of mass spectra of polymer additives using this technique is available. SFC-MS appears less performing than originally announced nevertheless, SFE-SFC-EIMS is an interesting niche approach to additive analysis. On the other hand, we notice the lack of real breakthrough in SFE-SFC-FTIR. 

Norton KL, Lange AJ, Griffiths PR. A unified approach to the chromatography-FTIR interface GC-FTIR, SFC-FTIR and HPLC-FTIR with subnanogram detection limits. HRC-J. High Resolut. Chromatogr. 1991 14 225-229. 

Non-ionic surfactants of a commercial washing powder were separated by supercritical fluid chromatography (SFC) and determined by APCI-MS. The constituents were first extracted by supercritical fluid extraction (SFE) using C02 with or without methanol as a modifier. Variations of the conditions resulted in a selective extraction of the analytes, which could be determined without further purification. Six groups of surfactants were observed, four of which are alkyl-polyethoxylates. The presence of APEO could be excluded by identification recording SFC-FTIR (Fourier transform infrared) spectra [31]. 

Figure 2. Gram-Schmidt Reconstruction obtained from SFE/SFC/FTIR of hexane fraction of Day 25 sample.

Jenkins T., Davidson G, PoliakofFM., Comparison ofXe and COi as Mobile Phase in On-Line SFC-FTIR Chromatographic Considerations, Journal of High Resolution Chromatography, Vol. 15, pp. 819-826, 1992... 

Note that Jenke " also cites references to the use of other related analytical techniques, including Head-space GC, high performance thin layer chromatography (HPTLC), supercritical fluid chromatography (SFC) /MS, and supercritical fluid chromatography/ Fourier transform infrared spectroscopy (SFC/FTIR). 

For HPLC-FTIR, GPC-FTIR, or SFC-FTIR, the design of the interface is more challenging since the mobile phases used for these chromatographic systems normally have strong infrared absorbencies thus, it is important to remove the mobile phase prior to measuring the spectrum. For the interface between the two systems flow-cells or mobile-phase elimination techniques may be used. Some recent developments point toward the elimination of mobile-phase techniques. A microbore column can help to reduce the mobile-phase volume in the system. ... 

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