Polymer glasses, ductility

Some of the most important early experimental observations were of transitions from the quasi-brittle crazing deformation mode to the ductile shear deformation mechanisms with changes in the experimental conditions, such as temperature and strain rate, as well as in polymer variables, such as polymer backbone architecture, blend composition, crosslinking and physical aging state of the polymer glass. One of the strengths of the model of craze growth outlined above is that it allows one to make sense out of some experimentally observed craze-to-shear transitions that had previously defied explanation . The idea behind this explanation is quite simple One writes an expression for the shear yield stress, viz ... 

Several cautions are, however, in order. Polymers are notorious for their time dependent behavior. Slow but persistent relaxation processes can result in glass transition type behavior (under stress) at temperatures well below the commonly quoted dilatometric or DTA glass transition temperature. Under such a condition the polymer is ductile, not brittle. Thus, the question of a brittle-ductile transition arises, a subject which this writer has discussed on occasion. It is then necessary to compare the propensity of a sample to fail by brittle crack propagation versus its tendency to fail (in service) by excessive creep. The use of linear elastic fracture mechanics addresses the first failure mode and not the second. If the brittle-ductile transition is kinetic in origin then at some stress a time always exists at which large strains will develop, provided that brittle failure does not intervene. 

Temperature dependence of shear modulus G and logarithmic decrement A as a function of temperature for poly(methyl methacrylate) at constant frequertcy near 1 Hz. The o-relaxation is due to the onset of movement of the main backtxxte of the molecule the j3-relaxation is due to the onset of hindered rotation of the side group. The polymer glass, at temperatures where the side group is mobile, is more ductile than at the lower temperatures when its movement is frozen in. Measurements taken by torsion perxlulum (after Schmieder and Wolf). 

It is tempting to relate the temperature at which the ductile-brittle transition takes place to either the glass transition or secondary transitions (Section 5.2.6) occurring within the polymer. In some polymers such as natural rubber or polystyrene Tb and Tg occur at approximately the same temperature. Many other polymers are ductile below the glass transition temperature (i.e. Tb < Tg). In this case it is sometimes possible to relate T to the occurrence of secondary low-temperature relaxations. However, more extensive investigations have shown that there is no general correlation between the brittle-ductile transition and molecular relaxations. This may not be too unexpected since these relaxations are detected at low strains whereas Tb is measured at high strains and depends upon factors such as the presence of notches which do not affect molecular relaxations. 

For thermoplastic polymers, both ductile and brittle modes are possible, and many of these materials are capable of experiencing a ductile-to-brittle transition. Factors that favor brittle fracture are a reduction in temperature, an increase in strain rate, the presence of a sharp notch, an increase in specimen thickness, and any modification of the polymer structure that raises the glass transition temperature (T ) (see Section 15.14). Glassy thermoplastics are brittle below their glass transition temperatures. However, as the temperature is raised, they become ductile in the vicinity of their T s and experience plastic yielding prior to fracture. This behavior is demonstrated by the stress-strain characteristics of poly(methyl methacrylate) (PMMA) in Figure 15.3. At 4°C, PMMA is totally brittle, whereas at 60°C it becomes extremely ductile. 

Some materials, like glass, have low and K, and crack easily ductile metals have high Gf and and are very resistant to fast-fracture polymers have intermediate G, but can be made tougher by making them into composites and (finally) many metals, when cold, become brittle - that is, G and fall with temperature. How can we explain these important observations ... 

Most successful composites combine the stiffness and hardness of a ceramic (like glass, carbon, or tungsten carbide) with the ductility and toughness of a polymer (like epoxy) or a metal (like cobalt). You will find all you need to know about them in Chapter 25. 

Polymers have a low stiffness, and (in the right range of temperature) are ductile. Ceramics and glasses are stiff and strong, but are catastrophically brittle. In fibrous... 

Other high performance polymer backbones have been explored as PEM materials in addition to poly-(arylene ether)s and polyimides. Ductile copolymers with high modulus and glass transition values are desirable PEM candidates. The hydrolytic and oxidative stability of many of these materials remains to be determined. Nevertheless, interesting synthetic methodologies have been employed to investigate these materials, which have been instructive in the search for new PEM candidates. 

Polycarbonates are an unusual and extremely useful class of polymers. The vast majority of polycarbonates are based on bisphenol A [80-05-7] (BPA) and sold under the trade names Lexan (GE), Makrolon (Bayer), Calibre (Dow), and Panlite (Idemitsu). BPA polycarbonates [25037-45-0]> having glass-transition temperatures in the range of 145—155°C, are widely regarded for optical clarity and exceptional impact resistance and ductility at room temperature and below. Other properties, such as modulus, dielectric strength, or tensile strength are comparable to other amorphous thermoplastics at similar temperatures below their respective glass-transition temperatures, T. Whereas below their Ts most amorphous polymers are stiff and britde, polycarbonates retain their ductility. 

Mechanical Properties. The room temperature modulus and tensile strength are similar to those of other amorphous thermoplastics, but the impact strength and ductility are unusually high. Whereas most amorphous polymers arc glass-like and brittle below their glass-transition temperatures, polycarbonate remains ductile to about — 10°C. The stress-strain curve for polycarbonate typical of ductile materials, places it in an ideal position for use as a metal replacement. Weight savings as a metal replacement are substantial, because polycarbonate is only 44% as dense as aluminum and one-sixth as dense as steel. 

STYRENE-MALEIC ANHYDRIDE. A thermoplastic copolymer made by the copolymerization of styrene and maleic anhydride. Two types of polymers are available—impact-modified SMA terpolymer alloys (Cadon ) and SMA copolymers, with and without rubber impact modifiers (Dylark ). These products are distinguished by higher heat resistance than the parent styrenic and ABS families. The MA functionality also provides improved adhesion to glass fiber reinforcement systems. Recent developments include lerpolymer alloy systems with high-speed impact performance and low-temperature ductile fail characteristics required by automotive instrument panel usage. 

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