title: Calibration models for the vinyl acetate concentration in ethylene-vinyl acetate copolymers and its on-line monitoring by near-infrared spectroscopy and chemometrics: use of band shifts associated with variations in the vinyl acetate concentration to improve the models.
abstract: The present study investigates calibration models for the vinyl acetate (VA) concentration in ethylene-vinyl acetate (EVA) copolymers and its on-line monitoring by near-infrared (NIR) spectroscopy and chemometrics. The key point in the present study is to make use of band shifts associated with concentration changes in the vinyl acetate (VA) for the improvement of the models. NIR spectra of EVA in melt and solid states were measured by a Fourier transform near-infrared (FT-NIR) on-line monitoring system and a FT-NIR laboratory system. Some of the bands in the NIR spectra for both states show significant shifts with the variations in the VA concentration. The peak shifts induced by the VA concentration changes are larger in the solid-state EVA than those in the melt-state EVA. We have developed calibration models for the VA concentration in the solid-state EVA and investigated how to improve the calibration models. The factor analysis of partial least squares (PLS) regression has suggested that the wavenumber shifts caused by the VA concentration changes affect the calibration models for the VA concentration in EVA. From the analysis, it has been proposed that the wavenumbers in the spectrum of one sample in nine EVA samples (VA concentration range: 0-41.1%) are shifted for the improvement of the calibration models, and the effects of the proposed method have been confirmed by using the PLS calibration models for the VA concentration in the solid EVA samples. As the next step, the effects of the wavenumber shift method have been explored for the calibration models for the VA concentration in the melt-state EVA. After that, the discrimination method using the score plots of PLS and the application sequence for the on-line monitoring to use the proposed wavenumber shift method were studied. The simulation results using the discrimination and wavenumber shift methods have shown that those methods are very effective to improve the predicted values of the calibration models for the on-line monitoring of the VA concentration in the melt-state EVA.
authors.affiliation: Environmental and Analytical Products Business Division, Yokogawa Electric Corporation, Musashino 180-8750, Japan.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Watari
authors.forename: Yukihiro
authors.initials: Y
authors.lastname: Ozaki
mesh_terms: D000465:Algorithms; D002138:Calibration; D020650:Combinatorial Chemistry Techniques / Q000379:methods*; D003198:Computer Simulation; D003199:Computer Systems; D007564:Japan; D008422:Materials Testing / Q000379:methods / Q000592:standards; D008956:Models, Chemical; D009862:Online Systems; D011145:Polyvinyls / Q000032:analysis* / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared / Q000295:instrumentation / Q000379:methods* / Q000592:standards*; D014753:Vinyl Compounds / Q000032:analysis* / Q000737:chemistry
chemical_list: D011145:Polyvinyls; D014753:Vinyl Compounds; C016438:ethylenevinylacetate copolymer; C011566:vinyl acetate