Spectroscopy polymer blends analysis

Polymer/additive analysis then usually proceeds by separation of polymer and additives (cf. Scheme 2.12) using one out of many solvent extraction techniques (cf. Chapter 3). After extraction the residue is pressed into a thin film to verify that all extractables have been removed. UV spectroscopy is used for verification of the presence of components with a chromophoric moiety (phenolic antioxidants and/or UV absorbers) and IR spectroscopy to verify the absence of IR bands extraneous to the polymer. The XRF results before and after extraction are compared, especially when the elemental analysis does not comply with the preliminary indications of the nature of the additive package. This may occur for example in PA6/PA6.6 blends where... 

Many studies use infrared spectroscopy for quality control and quality analysis in polymer production. It is particularly used for the determination of the composition of copolymers and polymer blends and also for determination of additive and filler contents [90, 91, 92]. 

The feasibility of diffuse reflectance NIR, Fourier transform mid-IR and FT-Raman spectroscopy in combination with multivariate data analysis for in/ on-line compositional analysis of binary polymer blends found in household and industrial recyclates has been reported [121, 122]. In addition, a thorough chemometric analysis of the Raman spectral data was performed. 

Radioluminescence spectroscopy has been used to examine molecular motion, solubility, and morphology of heterogeneous polymer blends and block copolymers. The molecular processes involved in the origin of luminescence are described for simple blends and for complicated systems with interphases. A relatively miscible blend of polybutadiene (PBD) and poly(butadiene-co-styrene) and an immiscible blend of PBD and EPDM are examined. Selective tagging of one of the polymers with chromophores in combination with a spectral analysis of the light given off at the luminescence maxima gives quantitative information on the solubility of the blend components in each other. Finally, it is possible to substantiate the existence and to measure the volume contribution of an interphase in sty-rene-butadiene-styrene block copolymers. 

Cheng and English edited ACS symposium series which covers the solution and solid state NMR investigations for dendrimers, cellulose, polyurethane, polyolefins biopolymers, copolymers and so on. Spiess described a historical overview of role of NMR spectroscopy in polymer science. Newmark summarizes the two dimensional and pulsed gradient diffusion NMR experiments and their applications to polymers Shit et al. reviewed the analysis of polymer molecular weight and copolymer composition by NMR. Sasanuma summarized the the analysis of polyethers and polysulfides by NMR and theoretical calcula-tions Ardelean et al described the principle and its applications of diffusion studies by NMR. Roy et al summarized the structural analysis of Novolak resins by multidimensional NMR. Reviews about NMR study of surfactant polymer blends and the structural elucidation of supramocules are published. 

In EP07708077A3 (Dabou et al. 1996), gas separation polymer membranes were prepared from mixtures of a polysulfone, Udel P-1700 and an aromatic polyimide, Matrimid 5218. The two polymers were proven to be completely miscible as confirmed by optical microscopy, glass transition temperature values and spectroscopy analysis of the prepared mixtures. This complete miscibility allowed for the preparation of both symmetric and asymmetric blend membranes in any proportion from 1 to 99 wt% of polysulfone and polyimide. The blend membranes showed significant permeability improvements, compared to the pure polyimides, with a minor change in the selectivity. Blend membranes were also considerably more resistant to plasticization compared with pure polyimides. This work showed the use of polysulfone-polyimide polymer blends for the preparation of gas separation membranes for applications in the separation of industrial gases. 

D IR spectroscopy has been applied extensively to studies of polymeric materials. A recent review of 2D IR spectroscopy cites numerous applications in the study of polymers by this technique [6]. In this section, some representative examples of 2D IR analysis of polymers are presented. We will start our discussion with a simple homogeneous amorphous polymer then move to more complex multiphase systems, such as semicrystalline polymers. Alloys and blends consisting of more than one polymer components are of great scientific and technical importance. Both immiscible and miscible polymer blend systems may be studied by 2D IR spectroscopy. Analysis of microphase-separated block copolymers is also possible. Finally, the possible application of 2D IR spectroscopy to the studies of natural polymers of biological origin is explored. 

Thermal analysis techniques are used to study the properties of polymers, blends and composites and to determine the kinetic parameters of their stability and degradation processes.Here the property of a sample is continuously measured as the sample is programmed through a predetermined temperature profile. Among the most common techniques are thermogravimetry (TG) and differential scanning calorimetry (DSC). Dynamic mechanical analysis (DMA) and dielectric spectroscopy are essentially extensions of thermal analysis that can reveal more subtle transitions with temperature as they affect the complex modulus or the dielectric function of the material. 

Generalized 2D NIR correlation spectroscopy has been appUed to study, for example, temperature-dependent spectral variations of various compounds such as A-methylacetamide (NMA) (34) and nylon 12 (29), concentration-dependent spectral changes in milk (18) and protein solntions at various temperatures (35, 36), composition-dependent spectral changes in polymer blends (37), and depth-dependent spectral variations of a polymer film (38). Examples of heterospectral correlation are 2D NlR-mid IR heterospectral correlation analysis of nylon 11 (39) and 2D NIR-Raman correlation analysis of polymer blends (40). 

There are specific structural and spatial problems in whieh Raman spectroscopy plays a dominant and important role based on higher sensitivity (due to resonance enhancement) and higher spatial resolution than FTIR. Specifically, micro-Raman spectroscopy has been applied in the analysis of (glass) fibres and their surface treatments, fibre composites, multilayer plastic films, foils and coatings, polymer blends, interfaces in eomposites, contaminant and paints/pigments [488]. 

Apart from phase discrimination (hard V5-. soft contents of materials), reports of chemical composition analysis by low-field H NMR spectroscopy are increasing. LR-NMR allows analysis of the soft-block content of (co)polymer blends in the solid state, as e.g. in polyesterethers and other thermoplastic elastomers. LR-NMR can also be applied... 

Rubber Chem. Technol., Rubber Rev. Degradation of Polymers (1962) Analysis, Composition and Structure of Rubber and Rubber Products (1967) Branching in Polymer Chains (1972) Applied Infrared Spectroscopy in the Rubber Industry (1972) Elastomer Blends (1974) Spectroscopy in the Rubber Industry (1976). 

---