Epoxy infrared spectroscopy

No epoxy groups were detectable in the cured polymer by infrared spectroscopy. 

To evaluate the reactivity of model compounds III-VIII in photoinitiated cationic polymerization, we have employed real-time infrared spectroscopy (RTIR). Thin film samples of the model compounds containing 0.5 mol% of (4-n-octyloxyphenyl)phenyliodonium SbF - as a photoinitiator were irradiated in a FTIR spectrometer at a UV intensity of 20 mW/cm2. During irradiation, the decrease in the absorbance of the epoxy ether band at 860 cm-1 was monitored. 

Fourier transform Infrared spectroscopy has been shown to be an excellent tool for surface and Interface studies (.2), In this paper, the application of reflection/absorption Fourier transform Infrared spectroscopy (FTIR-RA) for studying the degradation of amine-cured epoxy and polybutadiene coatings on cold-rolled steel after exposure to a warm, humid environment is reported. 

This article will review the impact of two powerful new techniques for characterizing epoxy resins at the molecular level — Fourier transform infrared spectroscopy (FT-IR) and high resolution nuclear magnetic resonance (NMR) of solids. Fortunately, these two techniques are not inhibited appreciably by the insoluble nature of the cured resin. Consequently, substantial structural information at the molecular level can be obtained. In this article, the basis of the methods will be briefly described in order to appreciate the nature of the methods followed by a description of the work on epoxies to date and finally some indication will be given of the anticipated contributions of these methods in the future. 

All of the usual sampling techniques used in infrared spectroscopy can be used with FT-IR instrumentation. The optics of the sampling chamber of commercial FT-IR instruments are the same as the traditional dispersive instruments so the accessories can be used without modification for the most part. To make full use of the larger aperature of the FT-IR instrument, some accessories should be modified to accomodate the larger beam. The instrumental advantages of FT-IR allow one to use a number of sampling techniques which are not effective using dispersive instrumentation. Transmission, diffuse reflectance and internal reflectance techniques are most often used in the study of epoxy resins. 

Antoon, M. K., Starkey, K. M., Koenig, J. L. Applications of Fourier Transform Infrared Spectroscopy to Quality Control of the Epoxy Matrix, Composite Materials, Fifth Conference, ASTM, p. 541, 1979... 

In this Sect, we describe the starting material impurities and their effect on the processing and cure reactions of TGDDM-DDS epoxies. The cure reactions are characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) studies. The BF3 amine catalysts used to accelerate the cure of TGDDM-DDS epoxies are characterized by nuclear magnetic resonance (NMR) spectroscopy studies. 

Many investigations of the molecular structure of thin films formed by y-APS deposited onto inorganic substrates from aqueous solutions have been carried out. Ondrus and Boerio [2] used reflection-absorption infrared spectroscopy (RAIR) to determine the structure of y-APS films deposited on iron, 1100 aluminum, 2024 aluminum, and copper substrates from aqueous solutions at pH 10.4. They found that the as-formed films absorbed carbon dioxide and water vapor to form amine bicarbonate salts which were characterized by absorption bands near 1330, 1470, 1570, and 1640 cm-1. y-APS films had to be heated to temperatures above about 90°C in order to dissociate the bicarbonates, presumably to free amine, carbon dioxide, and water. Since the amine bicarbonates failed to react with epoxies, the strength of adhesive joints prepared... 

Abstract—The structure of films formed by a multicomponent silane primer applied to an aluminum adherend and the interactions of this primer with an amine-cured epoxy adhesive were studied using X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, and attenuated total reflectance infrared spectroscopy. The failure in joints prepared from primed adherends occurred extremely close to the adherend surface in a region that contained much interpenetrated primer and epoxy. IR spectra showed evidence of oxidation in the primer. Fracture occurred in a region of interpenetrated primer and adhesive with higher than normal crosslink density. The primer films have a stratified structure that is retained even after curing of the adhesive. 

The best way to elucidate the reaction path is to follow the evolution of as many independent species and functional groups as possible. For example, analysis of the epoxy-amine reaction following the simultaneous evolution of epoxy and primary amine groups by near infrared spectroscopy (NIR) simultaneous determination of the conversion of double bonds belonging to unsaturated polyester (UP) and styrene (S) using FTIR, as shown in Fig. 5.13 (Yang and Lee, 1988) determination of the evolution of the concentration of free radicals using ESR, as shown in Fig. 5.14 (Tollens and Lee, 1993). 

O Brien and Hartman (26) studied the interface of a model system—epoxy resin, regenerated cellulose fibers—by attenuated total reflectance infrared spectroscopy. They compared spectra of the components to spectra of epoxy cured on cellulose and found for the mixture a diminished hydroxyl absorption (3,350 cm 1) and C-0 stretching (1,050 cm"1), and disappearance of the epoxy band (915 cm 1). From this they concluded that covalent bonding does occur between the epoxide groups and cellulose hydroxyls. 

An intermediate epoxy ketene (39) from a-cleavage of 2,5-diphenyl-3(2H)-furanone (40) has been proposed by Padwa and co-workers to explain photoisomerization to 4,5-diphenyl-2(5H)-furanone (47)38. The epoxy ketene was not observed when the irradiation was monitored by infrared spectroscopy and was not trapped by methanol. The authors suggest that the intermediate may be formed with excess vibrational energy and as a result undergo very rapid intramolecular reaction. 

Many different methods can be used to measure the degree of crosslinking within an epoxy specimen. These methods include chemical analysis and infrared and near infrared spectroscopy. They measure the extent to which the epoxy groups are consumed. Other methods are based on the measurements of properties that are directly or indirectly related to the extent and nature of crosslinks. These properties are the heat distortion temperature, glass transition temperature, hardness, electrical resistivity, degree of solvent swelling and dynamic mechanical properties, and thermal expansion rate. The methods of measurement are described in Chap. 20. 

The hydroxyl equivalent weight of epoxy resins can be determined by several methods. The most common is esterification with acids, reaction with acetyl chloride, and reaction with lithium aluminum hydride. Infrared spectroscopy may also be used. 

In the above model, data for the extent of reacticm at vitrification are needed. These data were obtained using infrared spectroscopy. The extent of conversion of the epoxy group was monitored as a function of time at a series of temperatures. A corresponding set of TBA experiments was performed, and the time to vitrification data were... 

Comparison of several techniques (namely Fourier transform infrared spectroscopy (FTIR), simultaneous thermogravimetric analysis-differential scanning calorimetry (TGA-DSC) and ultrasonic spectroscopy) for assessing the residual physical and mechanical characteristics of polymer matrix composites (PMCs) exposed to excessive thermal loads showed the measured power spectra of ultrasonic energy to correlate with performance of graphite fibre epoxy matrix composites exposed to thermal degradation, and also that analyses with the three techniques all pointed to the same critical temperature at which thermally induced damage increased sharply [58],... 

The first coupling of a LINAC with infrared spectroscopy has been performed by Palmese et al. in order to study in situ kinetics of radiation-induced cationic polymerization of epoxy systems. The aim of the study is to understand the curing behavior of polymers under irradiation. A UV light source and an electron beam (10 MeV pulse width of the beam from 2.5 to 10 pm) are coupled to a portable near infrared (NIR) instrument. Briefly, a portable NIR spectrometer (Control Development Incorporated, South Bend, IN, USA) is used,... 

Epoxy Resins by Near-Infrared Spectroscopy", SPE Transactions... 

Analysis of Cure. Infrared spectroscopy was utilized to examine film cure and the effect of stabilizers upon the cure of the epoxy acrylate. Pre-cured material has absorptions at 1635, 1410 and 810 cm-1 which clearly diminish after the resin is UV-irradiated (Figure 6). The 1635 cm-1 absorption can be assigned to the carbon-carbon stretch of an olefinic bond in conjugation with a carbonyl group the 1410 cm-1 can be assigned to the CH2 in-plane deformation of a vinylic group. The 810 cm-1 can also be assigned to some aspect of vinylic... 

Analysis. The kinetics of the light-induced cross-linking of EPI-based coatings was studied by infrared spectroscopy, by following the decrease upon UV exposure of the absorption bands characteristic of the related functional groups epoxy ring at 877 cm- vinyl ether and acrylate double bonds at 1628 and 812 cm- respectively. The degree of conversion (x) was calculated from the equation ... 

Characterization of the chemical structure of highly cross-linked polymers, and of the chemical changes that accompany degradation processes, relies on spectroscopic methods. Solid-state nuclear magnetic resonance techniques have the potential to allow a more detailed characterization than before possible of the chemical environment and structure of chemical crosslinks in elastomers and thermoset epoxies. Degradation processes in cross-linked systems have been studied by using infrared spectroscopy, solid-state NMR, and electron spin resonance. 

In addition to HPLC, elemental analysis, vapor phase osmometry. Fourier Transform Infrared Spectroscopy (FTIR), GC/MS, and NMR techniques were applied to verify the purity of the resin samples. Epoxy equivalent weights (EEW) were determined by the standard nonaqueous titration method (J ) using chloroform as the solvent. A correction for tertiary amine was obtained by conducting the titration in the absence of the quaternary halide. ... 

---