Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

Polymeric Materials
Introduction
(2009-Bt-Chem-21) The polymers are a diverse group of engineering materials. They are the main components of plastics, rubbers, resins, adhesives and paints. These materials have distinctive microstructures built from macromolecular chains and networks of carbon and other light elements. A polymer is a very large molecule in which one or two small units is repeated over and over again The small repeating units are known as monomers Imagine that a monomer can be represented by the letter A. Then a polymer made of that monomer would have the structure: -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-

Polymers are high molecular mass substance consisting of large number of repeating structural units. As polymers are single, giant molecules i.e. big size molecules, they are also called macromolecules. Simple molecules which combine to form polymers are called monomers. Process of formation of polymers from respective monomers is called polymerization.

Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

Most polymer materials are of organic composition that is they contain carbon, and are composed of large molecules (macromolecules) each built of many atoms. They include materials such as polyethylene, poly (vinyl chloride), polyamide and epoxy resins. Most polymer materials are of organic composition that is they contain carbon, and are composed of large molecules (macromolecules) each built of many atoms. They include materials such as polyethylene, poly (vinyl chloride), polyamide and epoxy resins. The molecular structure of polymers is responsible for many of the intriguing physical properties which lie behind their various applications. Polymers are composed of very large molecules (macromolecules) which consist of smaller units, called monomers, tightly bonded together with (strong) covalent bonds, for the case of a linear polymer chain. The chemical formula is of the type (A) n where A represents the monomer and the integer number n, called the degree of polymerisation or polymerisation index, is the number of monomers composing the chain. The length of the polymer chain (and the molar mass) is proportional to n. A linear polymer consists of a long linear chain of monomers. A branched polymer comprises a long backbone chain with several short side-chain branches covalently attached. Crosslinked polymers have monomers of one long or short chain covalently bonded with monomers of another short or long chain. Cross-linking results in a three-dimensional molecular network; the whole polymer is a giant macromolecule. Another useful classification of polymers is based on the chemical type of the monomers homopolymers consist of monomers of the same type; copolymers have different repeating units. Furthermore, depending on the arrangement of the types of monomers in the polymer chain, we have the following classification: the different repeating units are distributed randomly (random copolymer) or there are alternating sequences of the different monomers (alternating copolymers) in block copolymers long sequences of one monomer type are followed by long sequences of another type; and graft copolymers consist of a chain made from one type of monomer with branches of another type. -A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A

Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

Classification of polymers
(2009-Bt-Chem-21) The molecular structure of a fully polymerized polymer can be classified according to one of three major types: linear, branched, or crosslinked polymers.

Linear polymers
Linear chain does not imply straight molecules. They can curl, twist or fold. Linear molecules have higher densities) e.g. high density PE. In addition linear molecules have higher tensile strengths, higher stiffness, and higher softening temperature.

Branched polymers
Polymerization process may produce more complex structures branched. Branched molecules have more voids, lesser density, are more flexible & more permeable to gases and solvents than linear molecules

Cross-linked polymers
The bonding between two chains is called crosslinking occurs when monomers have more than have more than one double bond. Cross links make the sliding of polymer molecules very difficult. The polymer becomes very stiff and is very hard to deform. Fully cross-linked polymers are thermoset and do not show creep or relaxation, are usually brittle, and do not deform with heat. They decompose at high temperatures and fairly resistant. Polymers are generally classified according to their properties, and use as thermoplastic, thermosetting, and elastomers.

Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

Thermoplastics
Thermoplastics consist of flexible linear molecular chains that are tangled together like a plate of spaghetti or bucket of worms. As the name indicates, they soften when heated.

Thermosets
Thermosets remain rigid when heated and usually consist of a highly cross-linked, three-dimensional network.

Elastomers
Elastomers consist of linear polymer chains that are lightly cross-linked. Stretching an elastomer causes the chains to partially untangle but not deform permanently (like the thermoplastics).

Crystalline polymers
Areas in polymer where chains packed in regular way. Both amorphous and crystalline areas in same polymer. Crystalline regular chain structure no bulky side groups. More crystalline polymer stronger and less flexible.

Engineering properties of polymers

(2009-Bt-Chem-21)
Polymer materials are generally softer and weaker than metals and ceramics, but have distinctive engineering properties of great practical value.

Mechanical properties Elastic, viscous and viscoelastic response

The strain response of a material over the passage of time due to the application of a constant load is called creep. A purely elastic material responds instantaneously to the load and the strain remains constant; furthermore, it will recover its initial shape instantaneously upon the removal of the load. On the contrary, a viscous liquid will deform as long as the load

Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

continues to be applied. Upon removal of the load, the fluid does not return to its initial position. Fluids show a characteristic resistance to movement (flow), which is called viscosity. Viscosity results in a frictional energy loss, which dissipates in the fluid as heat. Polymeric materials behave both as viscous fluids and elastic solids. They are viscoelastic materials. The most important characteristic of viscoelastic materials is that their mechanical properties depend on time. The response of a viscoelastic material is intermediate between the solid and the liquid. There is usually an instantaneous elastic response followed by a delayed elastic response that could be followed by a purely viscous response. The creep recovery which follows upon the removal of the load starts with the immediate recovery of the instantaneous elastic response followed by the slow and gradual recovery of the delayed one; the viscous part does not recover. Creep and recovery depend on the applied load, molecular characteristics, microstructure and temperature.

Uniaxial tensile testing

 Amorphous thermoplastics are stiff and strong at temperatures below the glass transition temperature.  Thermosets, which are highly cross-linked networks, exhibit similar mechanical behaviour to glassy thermoplastics. At higher temperatures they also soften but never reach the state of viscous flow due to the cross-links which sustain cohesiveness.  Semi-crystalline polymers at room temperature are usually above glass transition and below the melting temperature, and for these reasons they are less stiff but tougher.  Elastomers above the glass transition (which is usually below 08C) are characterised by low elastic modulus but their main characteristic is the extremely high strains which can be attained. Recoverable deformations of 1000% are not unusual before strain hardening and failure. Although they never become completely viscous, in the vicinity and above glass transition, elastomers exhibit time-dependent behaviour and so-called retarded elasticity, i.e. viscoelasticity. At sufficiently low temperatures, they become glassy, i.e. stiff and brittle.

Creep
At high stresses the creep response of a polymeric material becomes non-linear and the creep compliance or modulus becomes a function of strain. Ultimately, after a period of creep (which can be very long) the polymer fails. Polymers can fail in various ways. Brittle fracture is usual for stiff/rigid and strong thermoplastics and thermosets while ductile yielding is the mechanical failure mode for semi-crystalline polymers. It has to be stressed again, though, that the behaviour can vary from these two extremes with temperature and strain rate in a dramatic fashion. Consequently, the mechanical properties are a function of temperature and time/frequency of deformation.

Molecular scale origins of mechanical behaviour

The time-dependent behaviour (creep, recovery, stress relaxation) is a direct consequence of the macromolecular character of the polymer molecules and the weak physical interactions between them (weak attractive van der Waals forces). The long polymer

Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

chains move/relax at slower rates compared to simple liquids. The mobility of long chains is due to a relatively slow serpent-like movement called reputation. The mechanical response of a material depends on the time it takes for its individual molecules to respond in the imposed deformation/stress, i.e. the molecular relaxation time. Crazing is a process which occurs only in polymer materials and is a direct consequence of their macromolecular nature.

Friction and wear resistance

Friction and wear are more complex materials properties. Abrasion/wear resistance in particular, which is directly associated to friction and strength, has great practical significance for durability. High molecular weight, semi crystalline polymers (e.g. high-density polyethylene (HDPE)) possesses toughness which usually provides excellent abrasion resistance. Rubbers generate high frictional forces (coefficient of friction 13) but they are susceptible to wear and they have to be reinforced with microscopic organic (e.g. carbon black) or inorganic (e.g. silica) particles in order to be used in engineering applications. On the other extreme, polytetrafluoroethylene (PTFE) exhibits very low friction (_0.030.15). In many cases the friction coefficient is a function of sliding speed.

Thermal properties
Polymers tend to expand readily as the temperature rises, and for unfilled polymers the linear thermal expansivity, _l, is generally an order of magnitude larger than for metals and ceramics. The thermal conductivity, _, can be very low because energy transfer between polymer chains or through polymer networks is inefficient. For this reason polymers are widely used for thermal insulation, especially in fibre or foam form. Specific heat capacity does not range widely.

Permeability
Most polymers are not porous (unless designed with a porous structure) and consequently show excellent barrier properties to gases, vapours and liquids. However, when polymers are used in the form of thin films and surface coatings, they cannot be considered impermeable.

Environmental resistance and durability

The environmental resistance which ultimately determines the durability of a component is a significant property of materials for engineering applications. The conjoint action is a crucial point because, for example, oxygen at moderate temperatures or sunlight induces thermal or photooxidation while at high temperatures the result is combustion. Water induces hydrolysis and heat alone produces pyrolysis. The combination of atmospheric oxygen, water and sunlight results in weathering and aging, while solvents and organic fluids induce softening and ultimately dissolution; the effect is exacerbated by heat.

Fire properties
Most polymeric materials are susceptible to relatively easy ignition above a critical temperature which leads to combustion, a rapid oxidation process which often involves the production of a flame.

Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

Biological attack
In contrast to natural polymers (cellulose, casein), most synthetic polymers are not susceptible to microbial microorganism (bacteria, fungi) attack. In the case of plasticised PVC, it has been shown that the biological attack does not result from the polymeric material but is due to the plasticiser used.

Toxicity
While solid polymers are not usually toxic at normal use temperature, their constituent monomers can be highly toxic and should be handled with care. Furthermore, potentially toxic monomers and other toxic gaseous substances can be released as products of pyrolysis and combustion. Moreover, many low molecular weight additives can present toxicity problems which have to be taken into account when polymers are to be used, e.g. in contact with potable water.

Applications of polymeric materials

(2009-Bt-Chem-06) Construction is one of the largest markets for polymer materials. A huge variety of plastics and rubbers find a multitude of uses. Among the most important are in pipes, geosynthetics, coatings and adhesives. Polymer materials do not generally compete with the main established metallic and ceramic load-bearing materials but, nonetheless, in recent decades have become indispensable in construction engineering. They offer a great range of valuable material properties, are generally softer in behaviour and able to tolerate large strains. Polymer-based materials have durability and performance attributes which contrast sharply with those of metals and ceramics. They are generally resistant to damage by water, but are prone to air oxidation and have poor fire performance. Here we survey briefly their uses in civil engineering.

Structural plastics and composites

Apart from pipes, large load-bearing components of unreinforced solid polymers are rarely found because of the low stiffness of these materials. Amorphous thermoplastics (PMMA, PC and PVC-U) are used to form roofing and cladding panels and as glazing.Polymer materials are also used for building panels, often of multi-layer sandwich construction to provide rigidity and thermal insulation.

Coatings
Surface coatings (paints) are widely used in the construction industry to protect timber surfaces and to prevent or reduce the corrosion of metals. Coatings may be applied on site or during manufacture or fabrication. In almost all these applications, polymer materials provide the coating film and bind the functional or decorative pigments which may be present. If the film is unpigmented and more or less transparent, the coating is often described as a varnish.

Department of Chemical Engineering, University of Engineering and Technology, KSK Campus, Lahore-Pakistan

Adhesives and sealants

Polymers are the basis of all engineering adhesives High-performance adhesives is formulated to set and develop strength by chemical reactions and so are thermoset materials. There are therefore similarities between adhesives and the matrix component of composite reinforced plastics (and indeed also between adhesives and paints). Thus structural glulam laminated timber (or indeed plywood) may be regarded as an adhesive bonded wood composite

Ropes and bars

Polymer materials achieve maximum stiffness when drawn to extend and orient the primary macromolecular chains. Some stiffening can also be achieved by stretching in two directions at right angles (biaxial orientation). Many semicrystalline thermoplastics are good fibre formers, notably the polyamides (PA), some polyesters, polyacrylonitrile (PAN) and polypropylene (PP).

Pipework
Large-diameter polymer pipes are used widely for water and gas distribution, drainage and sewerage, and for handling industrial effluents and slurriesMembranes and geosyntheticsPolymers are readily formed into continuous membranes, sheets, meshes and textiles, the use of which in civil engineering has been an important recent area of innovation. Thermoplastic textiles and meshes used primarily as soil reinforcement (geotextiles). There is also expanding use of polymer materials in tensile and air-supported roofing.

Expansion bearings and antivibration mounts

A minor but technically demanding use of polymers is in expansion bearings for bridge and pipeline construction. These may be fabricated either with a durable synthetic rubber such as polychloroprene CR (neoprene) or with a low-friction thermoplastic.Chemical grouts for soils Polymers based mainly on water-soluble acrylamide monomer have played a minor but long-established role in the stabilisation of soils or in reducing water permeability. To a large extent this technology has been superseded by the use of geosynthetics. Chemical grouts have also been used to control water infiltration in sewers
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