Glass transition expansion

The properties influenced include quantities such as viscosity, glass transition, expansion coefficients, and mechanical properties. 

Oxyhalide Glasses. Many glasses contain both oxide and haUde anions. The introduction of haUdes into an oxide glass typically serves to reduce the glass-transition temperature, T, and to increase the coefficient of thermal expansion. Oxyfluorophosphates have been investigated as laser host... 

Two resin systems based on this chemical concept are commercially available from Shell Chemical Company/Technochemie under the COMPIMIDE trademark COMPIMIDE 183 (34) [98723-11-2], for use in printed circuit boards, and COMPIMIDE 796 [106856-59-1], as a resin for low pressure autoclave mol ding (35). Typical properties of COMPIMIDE 183 glass fabric—PCB laminates are provided in Table 8. COMPIMIDE 183 offers a combination of advantageous properties, such as a high glass transition temperature, low expansion coefficient, and flame resistance without bromine compound additives. 

T and are the glass-transition temperatures in K of the homopolymers and are the weight fractions of the comonomers (49). Because the glass-transition temperature is directly related to many other material properties, changes in T by copolymerization cause changes in other properties too. Polymer properties that depend on the glass-transition temperature include physical state, rate of thermal expansion, thermal properties, torsional modulus, refractive index, dissipation factor, brittle impact resistance, flow and heat distortion properties, and minimum film-forming temperature of polymer latex... 

Thermal Properties. Thermal properties include heat-deflection temperature (HDT), specific heat, continuous use temperature, thermal conductivity, coefficient of thermal expansion, and flammability ratings. Heat-deflection temperature is a measure of the minimum temperature that results in a specified deformation of a plastic beam under loads of 1.82 or 0.46 N/mm (264 or 67 psi, respectively). Eor an unreinforced plastic, this is typically ca 20°C below the glass-transition temperature, T, at which the molecular mobility is altered. Sometimes confused with HDT is the UL Thermal Index, which Underwriters Laboratories estabflshed as a safe continuous operation temperature for apparatus made of plastics (37). Typically, UL temperature indexes are significantly lower than HDTs. Specific heat and thermal conductivity relate to insulating properties. The coefficient of thermal expansion is an important component of mold shrinkage and must be considered when designing composite stmctures. 

Glass transition Transition region or state in which an amorphous polymer changed from (or to) a viscous or rubbery condition to (or from) a hard and relatively brittle one. Transition occurs over a narrow temperature region similar to solidification of a liquid to a glassy state. This transformation causes hardness, brittleness, thermal expansibility, specific heat, and other properties to change dramatically. 

These techniques help in providing the following information specific heat, enthalpy changes, heat of transformation, crystallinity, melting behavior, evaporation, sublimation, glass transition, thermal decomposition, depolymerization, thermal stability, content analysis, chemical reactions/polymerization linear expansion, coefficient, and Young s modulus, etc. 

Results for the density, glass transition temperature, thermal expansion, rigidity, and yield strength are plotted according to Eq. (8.1) in Fig. 8.1. These properties remain proportional to each other. 

In order to simplify the procedure of evaluating the extent of mesophase and its mechanical and thermal properties, a simple but effective three-layer model may be used, which is based on measurements of the thermal expansions of the phases and the composite, below and above the transition zone of the composite, lying around its glass transition temperature Tgc. 

A simplified approach to the glass-transition temperature of the composite can be based on the thermal expansion curves of Fig. 2. The elastic filler (f) exhibits a... 

An additional check is the almost coincidence of the linear thermal expansion coefficients of the composite in the glassy region. Theory yields acl = 48.20 x 10-6 °C whereas experiment gives ac, = 48.00x 10 6 °C 1. This coincidence does not hold beyond glass transition. Indeed it was found that ot = 122.90 x 10-6 °C, whereas the experiment gave a 2 = 158 x 10"6 °C 1. 

As a consequence, the overall penetrant uptake cannot be used to get direct informations on the degree of plasticization, due to the multiplicity of the polymer-diluent interactions. The same amount of sorbed water may differently depress the glass transition temperature of systems having different thermal expansion coefficients, hydrogen bond capacity or characterized by a nodular structure that can be easily crazed in presence of sorbed water. The sorption modes, the models used to describe them and the mechanisms of plasticization are presented in the following discussion. 

The glass transition temperature of a dilute system, according to the free volume changes, is determined by the diluent volume fraction Vd, and changes of the thermal expansion coefficient, a, at Tg by using ... 

The free volume model seems to be more adequate to describe the plasticization behaviour of the systems of lower amine content. According to Eq. (5), the higher is the change of the expansion coefficient the lower is the influence of the diluent volume fraction. The three TGDDM-DDS mixtures cured with 20, 30 and 50 PHR of hardener were characterized l2) by changes of the expansion coefficient at the glass transition, respectively, of 0.63, 1.08 and 2.94x 10 3 °C l. The more dense and stiffer resin crosslinked with 50 PHR of DDS should be, in principle, the less... 

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. 

Items 1 and 2 are experimentally measurable, but it should be borne in mind that highly heat-resistant seals may come at, or near, their glass transition temperature (Tg) during a cooling event, and the coefficient of thermal expansion changes in this region. 

Since the glass transition corresponds to a constant value of the relaxation time [15], dTjdP is just the pressure coefficient of Tg. Comparing Equations 24.10 and 24.13, we see that the scaling exponent is related to quantities—thermal pressure coefficient, thermal expansion coefficient, Tg, and its pressure coefficient—that can all be determined from PVT measurements... 

Note that the linear coefficient of expansion, at is obtedned finm the slope of the straight fine. The glass softening point is also easily observed as is the glass transitional temperature (which is the point where the amorphous assy phase begins its transition to a crystalline phase. These glass-points can also be used to cross-check values obtained by the DTA method. 

The transition between crystalline and amorphous polymers is characterized by the so-called glass transition temperature, Tg. This important quantity is defined as the temperature above which the polymer chains have acquired sufficient thermal energy for rotational or torsional oscillations to occur about the majority of bonds in the chain. Below 7"g, the polymer chain has a more or less fixed conformation. On heating through the temperature Tg, there is an abrupt change of the coefficient of thermal expansion (or), compressibility, specific heat, diffusion coefficient, solubility of gases, refractive index, and many other properties including the chemical reactivity. 

The effect of physical aging on the crystallization state and water vapor sorption behavior of amorphous non-solvated trehalose was studied [91]. It was found that annealing the amorphous substance at temperatures below the glass transition temperature caused nucleation in the sample that served to decrease the onset temperature of crystallization upon subsequent heating. Physical aging caused a decrease in the rate and extent of water vapor adsorption at low relative humidities, but water sorption could serve to remove the effects of physical aging due to a volume expansion that took place in conjunction with the adsorption process. 

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