2. Structure and behavior of polymers 2.1, Some definitions in the field of polymers Polymers are very large organic molecules, so-called macromolecules. Their molar mass is usually {greater than 10.000 g/mol and ranges upward to almost infinitely high values, Many naturel products such as celllose, starch and proteins are polymers. Polymers have hoon made ashetietlly» for the Jest 100 years, These macroralecules are synthesized when monomers join together in cerain se. «quences ina polymerization reaction. Monomers are small eacive molecules, usually gaseous or lige uid under ambient conditions. The number of monomer units per macromolecule is related to the de- ree of polymerization. A pute monomer polymerizes to homopolymer, e.g, ethylene forms a polyethylene homopolymer. (cu-cn), Mixed monomers, eg ethylene and propylene, also form copolymers, in this ease an ethylene- propylene copolymer. A random distribution of the diffrent mononser unis leads to so-called random copolymers, The block copolymer consists ofa certain number of identical monomer blocks followed by blocks ofthe otter mosiomer. Finally, a graft copolymer is made by grafting sde chains on a mac- romolecue, Compared with metals the properties of polymers are strongly dependent on temperature. For this ea: soa, thermal analysis i very useful group of techniques for the characterization and identification of polymers. As with all organic matter, polymers decompose et elevated temperature ~ especialy in presence of oxygen, Polymers are classified ino thre groups: + Thermoplastis, «pastes» sch as polyethylene and polystyrene © Blastomers,erubber» suchas natural rubber and styrene-butadiene rubber ‘+ Thermoseis, such as unsatunted polyesters and epoxy resins Polymer mixtures (so-called binds) are also frequently used because this allows many important polymer properties to be optimized. Physical properties are also influenced by the orientation of the macromolecules as a result of molding, eg. injection molding or fiber spinning, Last but not least ‘quality is influenced through the use ofa wide range of additives Examples are © ilers such as chalk o earn black Reinforcing materials such as glass or carbon fibers ‘© Phasticizers Blowing agen © Antioxidants, UV and heat sabilizers Flame reisrdan Dyestuts, pigments Mold iubricas| were Tuso0 cates pteatons ‘eeorusmes age 192.2. Physical structure of polymers [At higher temperatures polymers exist as amogphous melts, This means thatthe macromolecules are present a trapped entanglemerts. The individual segments of the polymer chain exhibit a relatively large degree of mobility. Ith material is cooled so rapidly that it cannot erystallize, a stronely super- ‘ole amorphous mel is formed that on further cooling pases through the glass transition. An amor phous glass is formed. On cooling, molecular mobility decreases and the viscosity of the material in- fereases, The supercooled melt has often a highly viseous and frequently sticky consistency. At the sass transition, the vsoosty increases by several decades. Inthe glassy sate the material has the structure of an amorphous licuid bot the mechanical properties ofa sold. The reason for this behavior is tha, at the glass ransition, the cooperative molecular rearrangements typical for a liquid “reeze” so that only the vibrations typical fora solid remain. In practical tems, this means that below the glass transition temperature the polymer i hard and relatively brie Polymers stored between their melting temperature and glass transition temperature can undergo erys- tallization, Due to ther molecwar size and the chemically incorporated defects (chain ends and chain branching) , the polymer erystalites so formed differ markedly from the erystls of substances of low ‘molecular weight. Crystalites ae smal, imperfectly formed crystals. In the erystalization proces, the clongated molecules are forced fold Back on themselves (chain folding). The folded chains are often present as layers of lamellas benveen which amorphous material, or material that is no longer able to exytallize, i preset. Crystallize layers and amorphous layers allemate and form lamellar stzcks. The polymers are pay crystalline and parly amorphous and are refered to as semicrystalline polymers. ‘The polymer sinictures mentions ere shown schematically in the following diagram, amorphous semicrystalline mobile amorphous Since the erystallization of polymers frequently takes place relatively slowly, it ean be suppressed by ‘cooling rpidly to below the las transition temperature, A rule of thumb says that te glass transition temperature is about two-thirds of the melting temperature - measured in Kelvin, This rule applies to relatively large erytallites. [fan amorphous polymer tat is capable of crystallizing is heated to tem- peratures above the glass tansiion temperature, it can crystallize at relatively low temperatures. This type of erstallization i also known as cold crystallization “The melting temperature ofthe polymer crystallites depends on the crystal size. Thick lamsllas melt at higher temperattres than thin ores, The thickness ofthe lana depends not only on the erystalliza= tion temperature but also on the chemical structure ofthe chain, In this respect the distance between Page 20 ‘aerworastes erie TLeb0 cals peas @ a@ a icain branches and their Ingth is a very important factor. With polymers having a wide distribution of ‘Sie chain lengths and distances, a wide ringe of distribution of the sizeof the polymer erystalites can ‘cut. In this eas, very small and unstable erystallits thet melt shortly above the lass transition tem- perature can form next to relatively large stable erystalites. In such cases, a wide melting range is ob- Served, Tis type of behavior canbe observed with polyethylene (PE. [Apart fiom the crystallites themselves, semicrystalline polymers also contain amorphous regions. Be- ‘use of different degrees of mobiliy, one distinguishes between mobile amorphous and rigid amor [phous regions, The rigid arnorphous regions are found primarily atthe fold surfaces ofthe exystallits. ‘Movement i so restricted in thse regions that they do not participate in the glass transition ‘There are also polymers that ere unable to cystllze at all because of ther chemical structure, These polymers are always amorphcus. A good example is polystyrene (PS), where the styrene side chain {groups prevent crystallization 2.3. Thermoplastic polymers “Thermoplastic polymers melt o flow on heting. They consist of linear macromolecules that are either randomly coiled (amorphous termoplastics) or partly ondered as crystallites (semicrystalline thermao- plastics). Note: All the names and symbols of polymers mentioned in this booklet are wrtton according to 180 1083-1, 2.3.1. Amorphous plastics [clow their softening temporture (glas9 tansition temperature or glass temperature) , amorphous polymers are stiff or rigid some are Brit, e., polystyrene. On heating, they soften at their glass ran- ‘on temperature and become viscoelastic. On further eating, the viscosity decreases without a dis- tinct melting point becoming apparent The glass transition is influenced by the chemical structure of the monomer and the degree of polymerization. Polymers can therefore be chareeerized or identified by their glass transition temperature. The glass transition temperature is however lowered by the pres- ‘ence of plasticizers. Moisture san also act asa plasticizer. At the glass transition, the specific heat =~ pecity ofa polymer increases hy some 0.1 to 0.4 eK causing a step inthe DSC extve, Often, an endo- thermic pai (e so-called relasation peak) i visible inthe first heating run. This i caused by enthalpy relaxation occuring during stage at temperatures below the glas transition temperature Mere TUtb0caleced ppatne ‘aorusnes age