1 Plastics Materials

Kirk M. Cantor 1 and Patrick Watts 2 1 Plastics and Polymer Engineering Technology, Pennsylvania College of Technology, Williamsport, PA 17701, USA 2 Medcomp Inc., Harleysville, PA 19438, USA

1.1 Polymeric Materials 1.1.1 Long-Chain Molecules
All polymers used within the plastics industry have the same long-chain molecular structure. The only difference between the polymers is the repeat unit along the chain. Most of the time, the words “plastic” and “polymer” are used interchangeably in conversation. In actuality, these two terms refer to two separate states of the product. The term “plastic” comes from the Greek word “plastikos,” meaning “moldable.” The term caught on since the plastic products are molded into their final shape. The word “polymer” literally means “many parts.” Polymers are long, chain-like molecules comprised of a main base unit that repeats throughout the structure. Hundreds and even thousands of these units are repeated to form just one polymer chain. Plastic is made up of mostly polymer, but also contains such things as colorant and many other additives. Polymers can be classified as either being a thermoplastic polymer or a thermoset polymer (Figure 1.1). Thermoplastic polymers are composed of individual polymer chains. Thermosetting polymers crosslink and create a chemical bond between two separate polymer chains. These polymers are generally stronger than thermoplastic polymers after processing but cannot be reground and fed back into the process. Thermoplastics are more widely used in the plastics industry today due to their lower cost and relatively easy processing capabilities. However, thermosets are mostly utilized when a desired application requires very high strength and/or high heat resistance. Polymers are also classified by their semi-crystalline or amorphous state. Within a semi-crystalline polymer, there

are ordered regions known as crystals. The polymer chains align themselves into layers in some sections and remain amorphous (disordered) elsewhere. All polymers are completely amorphous in the melt state. Crystals form during cooling of the polymer. At present there are no polymers that are entirely comprised of crystals. Amorphous polymers do not contain any crystalline regions. The polymer chains remain in the random pattern that is created during processing. About half of the major polymers used today are amorphous and the others are semicrystalline. Figure 1.2 shows what crystalline regions look like compared to amorphous regions. There are two key transition temperatures for polymers. Amorphous regions of a polymer are frozen in place below the glass transition temperature (Tg). This is the critical temperature needed in order for the brittle, amorphous regions of the polymer to be able to flow. The second important temperature is the melt temperature (Tm). This is the point above which crystalline regions of a polymer are able to flow. Therefore, amorphous polymers only have a Tg and semi-crystalline polymers have both a Tg and a Tm. It is also important to know that the Tm of a semicrystalline polymer will be higher than its Tg. Thus, there may be flow (movement) present in the amorphous regions without flow occurring amongst the crystals. All types of molecules can be characterized by their molecular weight. Since polymers are molecules, we can also characterize them by their molecular weight. Polymers are formed by addition of repeat units. This allows for the molecular weight of a polymer to be an excellent indication of chain length as well. Since we know the molecular weight of the repeat unit, the chain length or total molecular weight

Figure 1.1 Thermoplastic vs. thermoset.
Applied Plastics Engineering Handbook Copyright Ó 2011 Elsevier Inc. All rights reserved.

Figure 1.2 Amorphous vs. semi-crystalline.


1. Crystal regions provide an added stiffness and increased toughness to the finished product. Most grocery bags are produced from PE. Figure 1.5).” Most of the time. During this stage. It is also able to be extrusion-processed. First. Viscosity is the resistance to flow. The term “polymerization” refers to the process of combining these monomers into very long chains which we know as “polymers. PE displays a wide range of properties that largely depends on its molecular weight. PE is also able to be extrusion-processed.2 Polypropylene Another common and relatively inexpensive polymer is polypropylene (PP). This is important in the polymerization process for the polymers. This provides needed strength for products and also a sense of elasticity to return to its original shape. It is also formed using addition polymerization. The chains can be aligned directionally. Similarly. increased crystallization also reduces clarity of the polymer. the monomers continue to attach to one 1.4 Polyethylene chemistry.5 Polypropylene repeat unit.1 Polyethylene Of the common polymers. this structure is comprised of a series of a repeating unit. or imbalanced. The reactions terminate by consuming all available monomer. 1. this is accomplished using heat and pressure (Figure 1. The two primary processes available today are addition polymerization and condensation polymerization. orientation is important within the creation of fibers. but a by-product. There are three stages to addition polymerization.2 Polymer Chemistry Everything has a molecular structure. Equal. another until the final stage occurs. PP generally has a lower percentage of crystallinity than PE but displays better strength and stiffness characteristics.1. A by-product of the reaction is condensed and released as the reaction occurs. the polymer chain is initiated by a catalyst of some sort and the chain begins to grow. PE is a semi-crystalline polymer. polyethylene (PE) is one of the better known and most used. Anisotropic. Entanglements also promote a polymer with a high melt viscosity.1.” Many of these monomers include a double bond between two carbon atoms and four pendant groups attached to these two carbons. However.6).2. but the propylene molecule is the monomer present (Figure 1. Figure 1.6 Polystyrene repeat unit.2. 1. the termination stage closes the polymer chain. The second step is the propagation phase. Condensation polymerization takes place as reactions occur within functional end groups. Addition polymerization occurs by the monomers simply being hooked on to one another with no by-products produced. However. Long chains also promote crystallization in semi-crystalline polymers. Lastly. 1.2. The long chains created within the polymerization process and through the use of repeat units provide some very important properties. Figure 1. Prior to becoming a repeat unit in a polymer chain. The large majority of the molecules in fibers are oriented in the same direction and create a strong tensile strength in that same direction. In its pure state. low-density polyethylene (LDPE) is more easily able to be extruded than high-density polyethylene (HDPE). In the case of polymers. biaxial orientation allows for excellent strength for films created in industry. in order to establish desired characteristics. .3 Polymerization.3 Polystyrene Polystyrene (PS) is polymerized through addition polymerization of styrene monomer (Figure 1.4). Figure 1.3). these small molecules were known as “monomers. This usually occurs by two growing chains combining to form one finished polymer chain.1. or oriented. such as H2O or HCl.4 A PPLIED P LASTICS E NGINEERING H ANDBOOK can be easily calculated by knowing one of these values. monomers attach to one another in condensation polymerization. Long-chain molecules create entanglements with each other. It is formed through addition polymerization of the ethylene monomer (Figure 1. is given off. Trading card collectors use polypropylene sheets to preserve the condition of their cards while showing them off.

but it is still able to be extruded.11 Polycarbonate repeat unit. 1.2. There are many different grades of Nylon. quenched to form amorphous PET (APET). 1. addition polymerization polymer. which is highly crystalline. It is most recognizable in computer housings.K IRK M. C ANTOR AND P.1.5 Polyamide Polyamide (PA) is a typical example of a condensation polymerized polymer in which H2O is released (Figure 1. PVC is generally a rigid polymer but can be made flexible by adding plasticizer. It is sometimes modified with rubber to provide improved impact toughness. meaning it absorbs moisture and must be dried prior to processing. PC has excellent strength.1.10 Acrylonitrile butadiene styrene chemistry. Figure 1.7). especially when chains are oriented.8). It is also hygroscopic. Figure 1.1.6 Polyethylene terephthalate Polyethylene terephthalate (PET) is another hygroscopic polymer (Figure 1. It is also semi-crystalline but can be Figure 1. WATTS 5 PS is stiff. Due to its great barrier properties. It is amorphous and hygroscopic.11). Figure 1.2.8 Nylon chemistry.9 Polyethylene terephthalate repeat unit. The three monomers that form the structure are present in the name (Figure 1.10). PET exhibits excellent strength properties.9). PA.2. or HIPS.7 Acrylonitrile butadiene styrene Acrylonitrile butadiene styrene (ABS) is a block. brittle. It is also used to make the white foam found in packaging products and cups. toughness. is hygroscopic. It has a relatively low flammability warning though.1. PET is widely used in the bottling industry. In the case of polyamide. It is addition polymerized.4 Polyvinyl chloride Polyvinyl chloride (PVC) is another extremely common amorphous polymer and is made from vinyl chloride (Figure 1. 1. 1. This modification produces high-impact polystyrene. It is polymerized through condensation polymerization with NaCl and H2O being released. It is also fairly easy to use in extrusion processing. 1. an amine group and an alcohol group of two monomers join to form an amide group. It is often used in manufacturing bulletproof windows and even lenses for eyeglasses.2. but it is thermally unstable which means it can degrade and release hazardous HCl gas. It is widely recognizable by its use in CD cases. Figure 1. and clear. and optical properties. PS is amorphous and thermoplastic.7 Polyvinyl chloride repeat unit. ABS is lightweight yet exhibits excellent strength properties. PA has low melt strength.2.1. generically known as Nylon. .8 Polycarbonate Polycarbonate (PC) is an amorphous polymer (Figure 1.

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