Polymeric Materials

M Buggy, University of Limerick, Ireland

r 2016 Elsevier Inc. All rights reserved.

Polymeric materials have been used from prehistoric times. Polymers are abundant in nature, found in all living systems, and
materials such as wood, paper, leather, natural fibers have found extensive use. While natural polymers retain their intrinsic
importance, today synthetic materials are mostly used. The first man-made polymers, formed by chemical modification of natural
materials, were produced in the second half of the nineteenth century. Fully synthetic polymers were developed in the twentieth
century, most in the period 1950–1970s driven by chemical industry expansion. These are the so-called plastics of modern society.
The feedstock for polymerization processes is petrochemical, and environmental concerns have led to more recent developments
of polymers from renewable resources.
A polymer molecule is large and generally consists of a chemical entity which is covalently bonded to its identical neighbors
and thus repeats along the length of molecule. The chemical entity is known as the repeat unit and it defines the specific polymer
under consideration. The repeat unit is usually formed from small molecules called monomers. Monomers must have a func-
tionality of two or more to produce a polymer. Those polymers which have the same repeat unit along the molecule are known as
homopolymers and these are the commonest polymeric materials. Copolymers, i.e., those with two or more different repeat units,
are important in some technical areas.
The idea of repeat units linked together to form the polymer has led to the concept of the chain molecule, which has been very
useful in modeling physical and mechanical properties. How individual polymer molecules move when supplied with thermal or
mechanical energy and how groups of molecules interact and entangle can explain the observed behavior. Big molecules behave
differently from small molecules. A sample of polymeric material will contain a large number of polymer molecules. The
production of each individual polymer molecule involves several thousand sequential chemical reactions. As this is large, the exact
number achieved for individual chains may be randomized giving polymer molecules of different sizes. The number of repeat
units along the molecule is known as the degree of polymerization. The product of the degree of polymerization and the relative
molar mass of the repeat unit defines the relative molar mass of the polymer molecule. Therefore, it is important to know the
average relative molar mass of a polymer sample and the distribution of relative molar masses.
The naming of polymeric materials can be problematic. There is a logically designed naming scheme from IUPAC but it is not
used extensively. Generally, generic names are used for most polymers. If the atoms in the repeat unit are the same as those of the
monomer feedstock, the polymer is called ‘polymonomer’, e.g., polypropylene, polystyrene. When the repeat unit is the product of
reacting two or more monomer molecules, the polymer is named by the linking group, e.g., polyester, polyamide. Most material is
sold under a branded name as a particular grade. The brand names are company specific and arbitrary and do not necessarily relate
to the generic name of the material. Also, the grading is not regulated. Thus, extrusion grade high impact polystyrene, bought from
two different suppliers may be two materials with somewhat different properties which will perform differently in specific
applications or processing.
Polymers have a wide range of physical and mechanical properties which suit a large number of technical applications.
Chemical structure, average relative molar mass and distribution, chain conformation, morphology, additives and reinforcing
fillers give a pallet of controls to define individual material properties envelope and allow sophisticated tailoring of material to
specific applications. Polymer process technology is mature and it is relatively easy to produce complex shapes from most
materials in a cost-effective way. As most polymers are low density materials, they have specific service advantage in transport
situations and substitution for metal has become important. Use of polymer membranes and media in battery and fuel cell
applications has grown. Polymeric materials dominate packaging applications and environmental pressures will ensure that
recycling and reuse of waste material will continue to be important development area. Healthcare equipment, medical devices, and
drug delivery systems have seen significant use and development of polymeric materials, particularly bio-absorbable systems.
Development of biomimetic polymers and analysis of structured molecular architectures has grown as the understanding of
natural polymers increased.
The Polymeric Materials section of the Reference Module in Materials Sciences and Materials Engineering is set up in a relatively
straightforward way. It starts with basic concepts as a clear understanding of chain molecules, types of polymer, and useful
polymer solutions. Polymer synthesis, chain growth and step growth polymerization as well as natural polymers are then
considered. Polymer processing is reviewed to include all standard melt and deformation processes. In-situ polymerization such as
reaction injection molding is also included. Polymer applications including those outlined above will be examined with a special
section on plastics recycling. The section includes overview articles as well as detailed up-to-date reviews. It is designed so that the
reader can enter the database at any point and search for specific information or use as general background reading.

Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.04104-7 1