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 nal 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 classied 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 classied 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 ow. The second important temperature is the melt temperature (Tm). This is the point above which crystalline regions of a polymer are able to ow. 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 ow (movement) present in the amorphous regions without ow 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 2011 Elsevier Inc. All rights reserved.

Figure 1.2 Amorphous vs. semi-crystalline.

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can be easily calculated by knowing one of these values. This is important in the polymerization process for the polymers. The long chains created within the polymerization process and through the use of repeat units provide some very important properties. Long-chain molecules create entanglements with each other. This provides needed strength for products and also a sense of elasticity to return to its original shape. Entanglements also promote a polymer with a high melt viscosity. Viscosity is the resistance to ow. The chains can be aligned directionally, or oriented, in order to establish desired characteristics. Equal, biaxial orientation allows for excellent strength for lms created in industry. Anisotropic, or imbalanced, orientation is important within the creation of bers. The large majority of the molecules in bers are oriented in the same direction and create a strong tensile strength in that same direction. Long chains also promote crystallization in semi-crystalline polymers. Crystal regions provide an added stiffness and increased toughness to the nished product. However, increased crystallization also reduces clarity of the polymer.

another until the nal stage occurs. Lastly, the termination stage closes the polymer chain. This usually occurs by two growing chains combining to form one nished polymer chain. Condensation polymerization takes place as reactions occur within functional end groups. A by-product of the reaction is condensed and released as the reaction occurs. The reactions terminate by consuming all available monomer.

1.1.2.1 Polyethylene
Of the common polymers, polyethylene (PE) is one of the better known and most used. It is formed through addition polymerization of the ethylene monomer (Figure 1.4). PE displays a wide range of properties that largely depends on its molecular weight. PE is also able to be extrusion-processed. However, low-density polyethylene (LDPE) is more easily able to be extruded than high-density polyethylene (HDPE). PE is a semi-crystalline polymer. Most grocery bags are produced from PE.

1.1.2 Polymer Chemistry

Everything has a molecular structure. In the case of polymers, this structure is comprised of a series of a repeating unit. Prior to becoming a repeat unit in a polymer chain, these small molecules were known as monomers. Many of these monomers include a double bond between two carbon atoms and four pendant groups attached to these two carbons. The term polymerization refers to the process of combining these monomers into very long chains which we know as polymers. Most of the time, this is accomplished using heat and pressure (Figure 1.3). The two primary processes available today are addition polymerization and condensation polymerization. Addition polymerization occurs by the monomers simply being hooked on to one another with no by-products produced. Similarly, monomers attach to one another in condensation polymerization, but a by-product, such as H2O or HCl, is given off. There are three stages to addition polymerization. First, the polymer chain is initiated by a catalyst of some sort and the chain begins to grow. The second step is the propagation phase. During this stage, the monomers continue to attach to one

1.1.2.2 Polypropylene
Another common and relatively inexpensive polymer is polypropylene (PP). It is also formed using addition polymerization, but the propylene molecule is the monomer present (Figure 1.5). PP generally has a lower percentage of crystallinity than PE but displays better strength and stiffness characteristics. It is also able to be extrusion-processed. Trading card collectors use polypropylene sheets to preserve the condition of their cards while showing them off.

1.1.2.3 Polystyrene
Polystyrene (PS) is polymerized through addition polymerization of styrene monomer (Figure 1.6). In its pure state,

Figure 1.4 Polyethylene chemistry.

Figure 1.5 Polypropylene repeat unit.

Figure 1.3 Polymerization.

Figure 1.6 Polystyrene repeat unit.

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PS is stiff, brittle, and clear. It is widely recognizable by its use in CD cases. It is also used to make the white foam found in packaging products and cups. PS is amorphous and thermoplastic. It is sometimes modied with rubber to provide improved impact toughness. This modication produces high-impact polystyrene, or HIPS.

Figure 1.9 Polyethylene terephthalate repeat unit.

1.1.2.4 Polyvinyl chloride

Polyvinyl chloride (PVC) is another extremely common amorphous polymer and is made from vinyl chloride (Figure 1.7). It is addition polymerized. PVC is generally a rigid polymer but can be made exible by adding plasticizer. It is also fairly easy to use in extrusion processing, but it is thermally unstable which means it can degrade and release hazardous HCl gas. It has a relatively low ammability warning though.

quenched to form amorphous PET (APET). PET exhibits excellent strength properties, especially when chains are oriented. Due to its great barrier properties, PET is widely used in the bottling industry.

1.1.2.7 Acrylonitrile butadiene styrene

Acrylonitrile butadiene styrene (ABS) is a block, addition polymerization polymer. The three monomers that form the structure are present in the name (Figure 1.10). It is amorphous and hygroscopic. ABS is lightweight yet exhibits excellent strength properties. It is most recognizable in computer housings.

1.1.2.5 Polyamide
Polyamide (PA) is a typical example of a condensation polymerized polymer in which H2O is released (Figure 1.8). In the case of polyamide, an amine group and an alcohol group of two monomers join to form an amide group. PA, generically known as Nylon, is hygroscopic, meaning it absorbs moisture and must be dried prior to processing. There are many different grades of Nylon, which is highly crystalline. PA has low melt strength, but it is still able to be extruded.

1.1.2.8 Polycarbonate
Polycarbonate (PC) is an amorphous polymer (Figure 1.11). It is polymerized through condensation polymerization with NaCl and H2O being released. It is also hygroscopic. PC has excellent strength, toughness, and optical properties. It is often used in manufacturing bulletproof windows and even lenses for eyeglasses.

1.1.2.6 Polyethylene terephthalate

Polyethylene terephthalate (PET) is another hygroscopic polymer (Figure 1.9). It is also semi-crystalline but can be

Figure 1.7 Polyvinyl chloride repeat unit.

Figure 1.10 Acrylonitrile butadiene styrene chemistry.

Figure 1.8 Nylon chemistry.

Figure 1.11 Polycarbonate repeat unit.