Crazing transition temperature

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. 

At intermediate temperature (between 10 and 80 °C for all the copolymers), two types of deformation are observed to coexist, i.e. crazes and SDZs. At temperatures just above the transition temperature, T12, from CSCs to mixed deformation, the crazes are of a high-aspect ratio, and the SDZs are generally restricted to the craze-bulk interfaces (Fig. 55a), al-... 

The fracture energy cannot be related to the failure of chemical bonds which may contribute only with a few Jm-2. Furthermore, the possibility of crazing is not allowed in thermosets because fibrils cannot exist due to the high crosslink density. So, in the case of high-Tg cross-linked materials the main source of energy absorption before failure is the yielding of the network. This assumption is obviously valid only above the ductile-brittle transition temperature (Fig. 12.5), where yielding is temperature-dependent. ... 

The acrylic plastics use the term acryl such as polymethyl methacrylate (PMMA), polyacrylic acid, polymethacrytic acid, poly-R acrylate, poly-R methacrylate, polymethylacrylate, polyethylmethacrylate, and cyanoacrylate plastics. PMMA is the major and most important homopolymer in the series of acrylics with a sufficient high glass transition temperature to form useful products. Repeat units of the other types are used. Ethylacrylate repeat units form the major component in acrylate rubbers. PMMAs have high optical clarity, excellent weatherability, very broad color range, and hardest surface of any untreated thermoplastic. Chemical, thermal and impact properties are good to fair. Acrylics will fail in a brittle manner, independent of the temperature. They will suffer crazing when loaded at stress about halfway to the failure level. This effect is enhanced by the presence of solvents. 

Kambour et al. performed extensive studies on the mechanisms of plasticization [18-25]. The correlation observed between the critical strain to craze and the extent of the glass-transition temperature (Tg) depression speaks strongly in favor of a mechanism of easier chain motion and hence easier void formation. In various studies on polycarbonate [19,24], polyphenylene oxide [20], polysulfone [21], polystyrene [22], and polyetherimide [25], Kambour and coauthors showed that the absorption of solvent and accompanying reduction in the polymer s glass-transition temperature could be correlated with a propensity for stress cracking. The experiments, performed over a wide range of polymer-solvent systems, allowed Kambour to observe that the critical strain to craze or crack was least in those systems where the polymer and the solvent had similar solubility values. The Hildebrand solubility parameter S [26] is defined as... 

The temperature distribution during crack propagation is shown in Fig. 15. As the crack advances, the heat continues to diffuse along the normal to the craze surfaces but the size of the hot zone remains comparable to that of the craze thickness. The maximum temperature increase is located at the crack/craze interface, where the craze thickening and related heat flux into the bulk are maxima. At this location, the temperature reaches the glass transition temperature Tg but plasticity is not enhanced in the bulk, which remains primarily elastic during crack propagation. 

The temperature distribution at craze breakdown and during crack propagation is shown in Fig. 17. As the crack advances, the temperature reaches the glass transition temperature at the location of the crack-craze transition, where plastic dissipation caused by craze thickening is maximum. However, this remains confined to a small volume around the crack-craze surfaces (see Fig. 17) so that no plasticity on a larger scale is promoted. 

Two families of transparent polycarbonate-silicone multiblock polymers based on the polycarbonates of bisphenol acetone (BPA) and bisphenol fluorenone (BPF) were synthesized. Incorporation of a 25% silicone block in BPA polycarbonate lowers by 100°C the ductile-brittle transition temperature of notched specimens at all strain rates silicone block incorporation also converts BPF polycarbonate into a ductile plastic. At the ductile-brittle transition two competing failure modes are balanced—shear yielding and craze fracture. The yield stress in each family decreases with silicone content. The ability of rubber to sustain hydrostatic stress appears responsible for the fact that craze resistance is not lowered in proportion to shear resistance. Thus, the shear biasing effects of rubber domains should be a general toughening mechanism applicable to many plastics. 

The plane stress yield zones that spread from the root of the notch envelope, distort, and neutralize the craze. At temperatures just below the ductile-brittle transition temperature the shear flow begins at the notch, but the craze breaks before the shear zones have grown enough to encompass the craze. 

Figure 19.13 shows the dynamic mechanical properties of such a blend of sPS with a mixture of Kraton G 1651 (15 %) and microsuspension rubber particles (20%) consisting of 60% butyl acrylate (BA) core grafted with 40% styrene shell (S//BA). The glass transition temperatures of the Kraton (-60 °C) and the butyl acrylate (-45 °C) phases can be easily distinguished from one another. The TEM image of such a product after deformation is shown in Figure 19.14. The annealed specimen is shown since the two rubber types are better discernible than in the nonannealed sample. As expected, crazing and voiding in the rubber particles dominate. The product had the following notched impact strengths (ISO 179/eA) injection moulded (80 °C mould temperature) 6.3, injection moulded (140 °C) 4.0 and annealed 3.7kJ/m2.

Above its glass transition temperature, shear processes dominate in sPS as was shown earlier. In Figure 19.15, the TEM images of deformed sPS modified with the core-shell modifier prepared using the microsuspension method are reproduced. At the surface of the specimen highly oriented rubber particle are discernible without voiding. In the inner part of the specimen, however, cavi-tated highly oriented particles have been formed. Crazes are not seen in the... 

Recently, Dettenmaier and Kausch have observed an intrinsic craze phenomenon in bisphenol-A polycarbonate (PC), drawn to high stresses and strains in a temperature region close to the glass transition temperature, T. This type of crazing is not only initiated under extremely well defined conditions which reflect specific intrinsic properties of the polymer but also produces numerous crazes of a very regular fibrillar structure. These crazes were called crazes II in order to distinguish them from the extrinsic type of craze, called craze I. As shown by the schematic representation in Figure 1, a detailed quantitative analysis of intrinsic crazes in terms of craze initiation and microstructure was possible. The basis of this analysis and the results obtained are reviewed in this article. 

In tensile tests at strain-rates of e = 2 x 10 -2 x 10" s" intrinsic crazing of PC has been observed in a temperature range of 120-135 °C, i.e. about 15-30 °C below the glass transition temperature Figure 2 shows a nominal stress-strain curve... 

Glass transition temperature Secondary transition Extension ratio Maximum extension ratio Craze intensification stress Craze initiation stress Tensile strength Compressive yield stress Drop in after yielding A measure of strain softening Test frequency... 

For craze growth at temperatures well below the glass transition temperature it is observed experimentally that the natural craze extension ratio X is nearly a constant value characteristic of the particular polymer under investigation It was ob-... 

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