Epoxy polymers glass transition temperatures

It was earlier shown that a layer of epoxy polymer on a metal siuface does not change the polymer condition [422, 423]. Treatment of the basalt surface with surfactant affects the glass-transition temperature of the polymer. As seen from Fig. 9.1, for a low-energy siuface (basalt, treated with surfactant) the polymer glass-transition temperature does not depend on variation of the thickness of the pol5rmer layer. 

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. 

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. 

The time and temperature dependent properties of crosslinked polymers including epoxy resins (1-3) and rubber networks (4-7) have been studied in the past. Crosslinking has a strong effect on the glass transition temperature (Tg), on viscoelastic response, and on plastic deformation. Although experimental observations and empirical expressions have been made and proposed, respectively, progress has been slow in understanding the nonequilibrium mechanisms responsible for the time dependent behavior. 

BMI polymers have glass transition temperatures in excess of 260°C and continuous-use temperatures of 200-230°C. BMI polymers lend themselves to processing by the same techniques used for epoxy polymers. They are finding applications in high-performance structural composites and adhesives (e.g., for aircraft, aerospace, and defense applications) used at tem-peratrues beyond the 150-180°C range for the epoxies. Bisnadimide (BNI) polymers are similar materials based on bisnadimides instead of bismaleimides. 

Much attention has been paid to the synthesis of fluorine-containing condensation polymers because of their unique properties (43) and different classes of polymers including polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, and epoxy prepolymers containing pendent or backbone-incorporated bis-trifluoromethyl groups have been developed. These polymers exhibit promise as film formers, gas separation membranes, seals, soluble polymers, coatings, adhesives, and in other high temperature applications (103,104). Such polymers show increased solubility, glass-transition temperature, flame resistance, thermal stability, oxidation and environmental stability, decreased color, crystallinity, dielectric constant, and water absorption. 

The dynamic mechanical properties of the siloxane-modified epoxy networks were also investigated. The DMTA curves for the control epoxy network exhibit the two major relaxations observed in most epoxy polymers 39 40,41>. A high temperature or a transition at 150 °C corresponds to the major glass transition temperature of the network above which large chain motion takes place. The low temperature or (5 transition is a broad peak extending from —90° to 0 °C with a center near —40 °C. It has been attributed predominantly to the motion of the CH2—CH(OH)—CH2—O (hydroxyether) group of the epoxy 39-40 2 ... 

With the initial glass transition temperature Tgp of the polymer in the dry state. It is limited in low-Tg epoxies and vinyl esters, but important in high-Tg amine-cured epoxies. 

Lin, C. H., Cai, S. X., and Lin, C. H., Flame-retardant epoxy resins with high glass-transition temperatures. II. Using a novel hexafunctional curing agent 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-yl-tris(4-aminophenyl) methane, J. Polym. Sci., Part A Polym. Chem., 2005, 43, 5971-5986. 

Tg is a property of a polymer that depends on its chemical composition and the degree of crosslinking or molecular interaction. Often the glass transition temperature is used as a measure of the degree of crosslinking in a specifically defined epoxy system. Adhesive... 

Epoxy resins may be blended with certain vinyl polymers to improve the impact strength and peel strength of the adhesive. Polyvinyl acetals, such as polyvinyl butyral and polyvinyl formal, and polyvinyl esters are compatible with DGEBA epoxy resins when added at concentrations of 10 to 20% by weight. The addition improves the resulting impact resistance and peel strength of the cured adhesive. However, temperature and chemical resistance are sacrificed by the addition of the low-glass-transition-temperature vinyl resins. 

---