Glass transition temperature, cured resins

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. 

The overall picture which emerges is that the presence of rubber influences the glass transition temperature of resin. The fact that the Tg of the rubber for PER/PBNCO post cured resin is larger than that of pristine PBNCO may be accounted for by a reduction of free volume related to the formation of the A-B A copolymer. 

Elastomeric Modified Adhesives. The major characteristic of the resins discussed above is that after cure, or after polymerization, they are extremely brittie. Thus, the utility of unmodified common resins as stmctural adhesives would be very limited. Eor highly cross-linked resin systems to be usehil stmctural adhesives, they have to be modified to ensure fracture resistance. Modification can be effected by the addition of an elastomer which is soluble within the cross-linked resin. Modification of a cross-linked resin in this fashion generally decreases the glass-transition temperature but increases the resin dexibiUty, and thus increases the fracture resistance of the cured adhesive. Recendy, stmctural adhesives have been modified by elastomers which are soluble within the uncured stmctural adhesive, but then phase separate during the cure to form a two-phase system. The matrix properties are mosdy retained the glass-transition temperature is only moderately affected by the presence of the elastomer, yet the fracture resistance is substantially improved. 

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. 

Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to measure the glass transition temperatures (Tgs) of the uncured and cured AT-resins respectively (Figure 6). 

Figure 6. AT-Resin Initial and Cured Glass Transition Temperatures (Tgs).

Yamani and Young (5) applied the theory to explain the plastic deformation of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin cured with various amount of triethylene tetramine (TETA). They found that the theory gave a reasonable description for the resins below the glass transition temperatures T. ... 

Glass transition temperatures (Tg s) were detemined using a Dupont DSC 910 attached to a 9900 data analysis system. For off-stoichiometric studies, epoxy resin and diamine were cured in situ within a hermetically sealed DSC pan (sample tak from 25 C - 300 C at lO C/min), then cooled rapidly back to 25 C, and finally scanned from 40 C - 220 c to record the Tg. All samples were scanned under nitrogen atmosphere at a rate of 10 C/min. 

Figure lA. Glass transition temperature (Tg) and molecular weight between crosslinks (Me) as a function of epoxy/amine ratio for C-stage cured neat resin. 

Bulk Properties of Cured Resin. Table I presents glass transition temperature (Tg) and the coefficients of expansion values obtained for each sample. 

The glass transition temperatures, specific for each thermosetting resin, are used to characterize cure kinetics. They can be measured by many techniques, of which the widely used are Differential Scanning Calorimetry (DSC) and Torsional Braid Analysis (TBA)... 

The glass transition temperature for the totally cured resin is 130°C. 

The heating rates were 1, 5 and 10°C/min. The glass transition temperature of the cured resins was determined at 20°C/min. 

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