Epoxy structure, characterization

The application of FT-IR and high resolution solid state NMR to the structural characterization of epoxies is described. Theoretical and experimental background is given and progress to date in these two fields summarized. 

The microstructure of epoxy thermosets can be complex, and both molecular and physical microstructures are presumed. Unfortunately, the intractable nature of these materials makes direct structural characterization extremely difficult. The most accessible technique for direct structural characterization is evaluation of epoxy rubber-like properties above Tg. Sometimes, indirect characterization of epoxy structure is possible due to the fact that the chemistry of several epoxy systems is well behaved (e.g., epoxy-amine chemistry). This permits epoxy network structure to be modeled accurately as a function of the extent of the crosslinking reaction(s). This approach has been developed extensively by Du ek and coworkers for amine-linked epoxies ... 

Amine light stabilizer, melamlne-acryllo copolymer degradation, 281-83 Amine-cured epoxy networks cross-link density, 166-67,177-81 structure characterization, 172-73... 

There are many examples in the literature of the structural characterization of polymeric systems by FD-MS. Some of these will be briefly mentioned here. Saito and coworkers in Japan have studied a number of polymers by FD-MS. FD spectra were used to identify various poly(ethylene glycol) and poly(pro-pylene glycol) initiators (water, ethyleneimine, glycerol, sorbitol, sucrose). Structures of bisphenol A-based epoxy resins were elucidated. The degree of methylation in methylol melamine resins was assessed. Various novalak resins (made from phenol, alkylphenols, and epoxidized phenols) were characterized. Styrene polymerized with various initiators and chain transfer agents was studied in some cases deuterium labeling was used to help... 

Mechanical property characterization involves measurement of fiacture energy, stress intensity, tensile strength and modulus, and tan. Tan (9) can be defined as the ratio of the loss modulus, E", to the in-phase or storage modulus, E. Tan = E7E. Values for tan obtained from dynamic mechanical analysis can be related to epoxy structure. 

In a contribution from B. F. Goodrich, Drake and Siebert extensively review the journal and patent literature since 1975 on reactive butadiene/acrylonitrile liquid and solid elastomers used in formulating epoxy structural adhesives. Areas reviewed include the preparation of elastomer-modified epoxy resins, the characterization of rubber-toughened epoxy resins, fracture mechanics and adhesive formulation and testing. 

The two-component urethane structural adhesives are among the most difficult to characterize, simply because of the widely varying properties that are possible. These adhesives may be rigid plastics similar in modulus to standard epoxy adhesives, with glass transition temperatures of the cured adhesive being approximately 60°C. 

The structure of the products were characterized by two detector gel-chromatography (recractometer and UV). The direction of the alkylation reaction of toluene with EC was changed depending on the reaction condition as follows if the ratio of toluene-EC is 1 5 mol, the alkylation reaction is toward obtaining the PEC at 273 K and if the ratio is reverse at 333 K, the reaction undergone to obtain epoxy toluene oligomer is shown in Fig. 1. 

Water molecules combine the tendency to cluster, craze and plasticize the epoxy matrices with the characteristic of easily diffusion in the polymer1 10). The morphology of the thermoset may be adversaly influenced by the presence of the sorbed moisture. The diffusion of the water in glassy polymers able to link the penetrant molecules is, therefore, characterized by various mechanisms of sorption which may be isolated giving useful information on the polymer fine structure. 

Network properties and microscopic structures of various epoxy resins cross-linked by phenolic novolacs were investigated by Suzuki et al.97 Positron annihilation spectroscopy (PAS) was utilized to characterize intermolecular spacing of networks and the results were compared to bulk polymer properties. The lifetimes (t3) and intensities (/3) of the active species (positronium ions) correspond to volume and number of holes which constitute the free volume in the network. Networks cured with flexible epoxies had more holes throughout the temperature range, and the space increased with temperature increases. Glass transition temperatures and thermal expansion coefficients (a) were calculated from plots of t3 versus temperature. The Tgs and thermal expansion coefficients obtained from PAS were lower titan those obtained from thermomechanical analysis. These differences were attributed to micro-Brownian motions determined by PAS versus macroscopic polymer properties determined by thermomechanical analysis. 

Siloxane containing interpenetrating networks (IPN) have also been synthesized and some properties were reported 59,354 356>. However, they have not received much attention. Preparation and characterization of IPNs based on PDMS-polystyrene 354), PDMS-poly(methyl methacrylate) 354), polysiloxane-epoxy systems 355) and PDMS-polyurethane 356) were described. These materials all displayed two-phase morphologies, but only minor improvements were obtained over the physical and mechanical properties of the parent materials. This may be due to the difficulties encountered in controlling the structure and morphology of these IPN systems. Siloxane modified polyamide, polyester, polyolefin and various polyurethane based IPN materials are commercially available 59). Incorporation of siloxanes into these systems was reported to increase the hydrolytic stability, surface release, electrical properties of the base polymers and also to reduce the surface wear and friction due to the lubricating action of PDMS chains 59). 

Well-defined complicated macromolecular structures require complex synthetic procedures/techniques and characterization methods. Recently, several approaches leading to hyperbranched structures have been developed and will be the focus of this section. The preparation of hyperbranched poly(siloxysilane) has been reported [198] and is based on methylvinyl-bis(dimethyl siloxysilane), an A2B type monomer, and a progressive hydrosi-lylation reaction with platinum catalysts. An appropriate hydrosilylation reaction on the peripheral - SiH groups led to the introduction of polymeric chain (PIB, PEO) or functional groups (epoxy, - NH2) [199]. 

The measured G(x) value of representative epoxy polymers is approximately 10, but this value depends strongly on the structure of the polymer, its glass transition temperature and other characteristics. Since the crosslinking reaction that characterizes the COP resist functionality is a chain reaction, in theory, a single, electron-initiated event could result in the insolublization of an entire film of the resist material. Fortunately, because of the existence of chain terminating reactions, this does not occur and high resolution imaging of the resist material can be accomplished. 

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. 

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... 

The cycloaliphatic epoxy resins are characterized by the saturated ring in their chemical structure. They are almost water-white, very low-viscosity liquids. They provide excellent electrical properties such as low dissipation factor and good arc-track resistance, good weathering, and high heat distortion temperature. They are also free of hydrolyzable chlorine, sometimes present in DGEBA resins, which adversely affects certain electronic applications. 

---