A polymer (; Greek ''

poly- Poly, from the Greek :wikt:πολύς, πολύς meaning "many" or "much", may refer to: Businesses * China Poly Group Corporation, a Chinese business group, and its subsidiaries: ** Poly Property, a Hong Kong incorporated Chinese property devel ...

'', "many" + ''

-mer {{Short pages monitor The structure of a polymeric material can be described at different length scales, from the sub-nm length scale up to the macroscopic one. There is in fact a hierarchy of structures, in which each stage provides the foundations for the next one. The starting point for the description of the structure of a polymer is the identity of its constituent monomers. Next, the microstructure essentially describes the arrangement of these monomers within the polymer at the scale of a single chain. The microstructure determines the possibility for the polymer to form phases with different arrangements, for example through

crystallization Crystallization is the process by which solid forms, where the atoms or molecules are highly organized into a structure known as a crystal. Some ways by which crystals form are precipitating from a solution, freezing, or more rarely deposi ...

, the

glass transition The glass–liquid transition, or glass transition, is the gradual and reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle "glassy" state into a viscous or rubb ...

or microphase separation. These features play a major role in determining the physical and chemical properties of a polymer.

Monomers and repeat units

The identity of the repeat units (monomer residues, also known as "mers") comprising a polymer is its first and most important attribute. Polymer nomenclature is generally based upon the type of monomer residues comprising the polymer. A polymer which contains only a single type of repeat unit is known as a homopolymer, while a polymer containing two or more types of repeat units is known as a copolymer. A terpolymer is a copolymer which contains three types of repeat units.

Polystyrene Polystyrene (PS) is a synthetic polymer made from monomers of the aromatic hydrocarbon styrene. Polystyrene can be solid or foamed. General-purpose polystyrene is clear, hard, and brittle. It is an inexpensive resin per unit weight. It is a ...

is composed only of styrene-based repeat units, and is classified as a homopolymer.

Polyethylene terephthalate Polyethylene terephthalate (or poly(ethylene terephthalate), PET, PETE, or the obsolete PETP or PET-P), is the most common thermoplastic polymer resin of the polyester family and is used in fibres for clothing, containers for liquids and foods ...

, even though produced from two different monomers ( ethylene glycol and

terephthalic acid Terephthalic acid is an organic compound with formula C6H4(CO2H)2. This white solid is a commodity chemical, used principally as a precursor to the polyester PET, used to make clothing and plastic bottles. Several million tonnes are produced annua ...

), is usually regarded as a homopolymer because only one type of repeat unit is formed.

Ethylene-vinyl acetate Ethylene-vinyl acetate (EVA), also known as poly (ethylene-vinyl acetate) (PEVA), is the copolymer of ethylene and vinyl acetate. The weight percent of vinyl acetate usually varies from 10 to 40%, with the remainder being ethylene. There are th ...

contains more than one variety of repeat unit and is a copolymer. Some biological polymers are composed of a variety of different but structurally related monomer residues; for example, polynucleotides such as DNA are composed of four types of nucleotide subunits. : A polymer containing ionizable subunits (e.g., pendant carboxylic groups) is known as a polyelectrolyte or ionomer, when the fraction of ionizable units is large or small respectively.

Microstructure

The microstructure of a polymer (sometimes called configuration) relates to the physical arrangement of monomer residues along the backbone of the chain. These are the elements of polymer structure that require the breaking of a covalent bond in order to change. Various polymer structures can be produced depending on the monomers and reaction conditions: A polymer may consist of linear macromolecules containing each only one unbranched chain. In the case of unbranched polyethylene, this chain is a long-chain ''n''-alkane. There are also branched macromolecules with a main chain and side chains, in the case of polyethylene the side chains would be alkyl groups. In particular unbranched macromolecules can be in the solid state semi-crystalline, crystalline chain sections highlighted red in the figure below. While branched and unbranched polymers are usually thermoplastics, many

elastomer An elastomer is a polymer with viscoelasticity (i.e. both viscosity and elasticity) and with weak intermolecular forces, generally low Young's modulus and high failure strain compared with other materials. The term, a portmanteau of ''elastic p ...

s have a wide-meshed cross-linking between the "main chains". Close-meshed crosslinking, on the other hand, leads to thermosets. Cross-links and branches are shown as red dots in the figures. Highly branched polymers are amorphous and the molecules in the solid interact randomly. :

Polymer architecture

An important microstructural feature of a polymer is its architecture and shape, which relates to the way branch points lead to a deviation from a simple linear chain. A

branched polymer In polymer chemistry, branching is the regular or irregular attachment of side chains to a polymer's backbone chain. It occurs by the replacement of a substituent (e.g. a hydrogen atom) on a monomer subunit by another covalently-bonded ch ...

molecule is composed of a main chain with one or more substituent side chains or branches. Types of branched polymers include

star polymer Star-shaped polymers are the simplest class of branched polymers with a general structure consisting of several (at least three) linear chains connected to a central core. The core, or the center, of the polymer can be an atom, molecule, or macr ...

s, comb polymers, polymer brushes, dendronized polymers, ladder polymers, and dendrimers. There exist also

two-dimensional polymer A two-dimensional polymer (2DP) is a sheet-like monomolecular macromolecule consisting of laterally connected repeat units with end groups along all edges. This recent definition of 2DP is based on Hermann Staudinger's polymer concept from the 1 ...

s (2DP) which are composed of topologically planar repeat units. A polymer's architecture affects many of its physical properties including solution viscosity, melt viscosity, solubility in various solvents, glass-transition temperature and the size of individual polymer coils in solution. A variety of techniques may be employed for the synthesis of a polymeric material with a range of architectures, for example living polymerization.

Chain length

A common means of expressing the length of a chain is the degree of polymerization, which quantifies the number of monomers incorporated into the chain.Rubinstein, p. 3 As with other molecules, a polymer's size may also be expressed in terms of molecular weight. Since synthetic polymerization techniques typically yield a statistical distribution of chain lengths, the molecular weight is expressed in terms of weighted averages. The

number-average molecular weight The molar mass distribution (or molecular weight distribution) describes the relationship between the number of moles of each polymer species (Ni) and the molar mass (Mi) of that species. In linear polymers, the individual polymer chains rarely h ...

(''M''_n) and

weight-average molecular weight The molar mass distribution (or molecular weight distribution) describes the relationship between the number of moles of each polymer species (Ni) and the molar mass (Mi) of that species. In linear polymers, the individual polymer chains rarely hav ...

(''M''_w) are most commonly reported.Rubinstein, pp. 23–24 The ratio of these two values (''M''_w / ''M''_n) is the dispersity (''Đ''), which is commonly used to express the width of the molecular weight distribution. The physical properties of polymer strongly depend on the length (or equivalently, the molecular weight) of the polymer chain.Rubinstein, p. 5 One important example of the physical consequences of the molecular weight is the scaling of the viscosity (resistance to flow) in the melt. The influence of the weight-average molecular weight (

M_w

) on the melt viscosity (

\eta

) depends on whether the polymer is above or below the onset of entanglements. Below the entanglement molecular weight,

\eta \sim ^

, whereas above the entanglement molecular weight,

\eta \sim ^

. In the latter case, increasing the polymer chain length 10-fold would increase the viscosity over 1000 times. Increasing chain length furthermore tends to decrease chain mobility, increase strength and toughness, and increase the glass-transition temperature (T_g). This is a result of the increase in chain interactions such as van der Waals attractions and entanglements that come with increased chain length. These interactions tend to fix the individual chains more strongly in position and resist deformations and matrix breakup, both at higher stresses and higher temperatures.

Monomer arrangement in copolymers

Copolymers are classified either as statistical copolymers, alternating copolymers, block copolymers, graft copolymers or gradient copolymers. In the schematic figure below, Ⓐ and Ⓑ symbolize the two repeat units. : *Alternating copolymers possess two regularly alternating monomer residues:Painter, p. 14 . An example is the equimolar copolymer of styrene and maleic anhydride formed by free-radical chain-growth polymerization.Rudin p.18-20 A step-growth copolymer such as Nylon 66 can also be considered a strictly alternating copolymer of diamine and diacid residues, but is often described as a homopolymer with the dimeric residue of one amine and one acid as a repeat unit.Cowie p.104 *Periodic copolymers have more than two species of monomer units in a regular sequence. *Statistical copolymers have monomer residues arranged according to a statistical rule. A statistical copolymer in which the probability of finding a particular type of monomer residue at a particular point in the chain is independent of the types of surrounding monomer residue may be referred to as a truly random copolymer.Painter, p. 15 For example, the chain-growth copolymer of vinyl chloride and vinyl acetate is random. *Block copolymers have long sequences of different monomer units. Polymers with two or three blocks of two distinct chemical species (e.g., A and B) are called diblock copolymers and triblock copolymers, respectively. Polymers with three blocks, each of a different chemical species (e.g., A, B, and C) are termed triblock terpolymers. *Graft or grafted copolymers contain side chains or branches whose repeat units have a different composition or configuration than the main chain. The branches are added on to a preformed main chain macromolecule. Monomers within a copolymer may be organized along the backbone in a variety of ways. A copolymer containing a controlled arrangement of monomers is called a sequence-controlled polymer. Alternating, periodic and block copolymers are simple examples of sequence-controlled polymers.

Tacticity

Tacticity describes the relative

stereochemistry Stereochemistry, a subdiscipline of chemistry, involves the study of the relative spatial arrangement of atoms that form the structure of molecules and their manipulation. The study of stereochemistry focuses on the relationships between stereois ...

of chiral centers in neighboring structural units within a macromolecule. There are three types of tacticity: isotactic (all substituents on the same side), atactic (random placement of substituents), and syndiotactic (alternating placement of substituents). :

Morphology

Polymer morphology generally describes the arrangement and microscale ordering of polymer chains in space. The macroscopic physical properties of a polymer are related to the interactions between the polymer chains. * Disordered polymers: In the solid state, atactic polymers, polymers with a high degree of branching and random copolymers form

amorphous In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal. Etymology The term comes from the Greek ''a'' ("wi ...

(i.e. glassy structures).Bernd Tieke: ''Makromolekulare Chemie.'' 3. Auflage, Wiley-VCH, Weinheim 2014, S. 295f (in German). In melt and solution, polymers tend to form a constantly changing "statistical cluster", see freely-jointed-chain model. In the

solid state Solid state, or solid matter, is one of the four fundamental states of matter. Solid state may also refer to: Electronics * Solid-state electronics, circuits built of solid materials * Solid state ionics, study of ionic conductors and their u ...

, the respective conformations of the molecules are frozen. Hooking and entanglement of chain molecules lead to a "mechanical bond" between the chains. Intermolecular and intramolecular attractive forces only occur at sites where molecule segments are close enough to each other. The irregular structures of the molecules prevent a narrower arrangement. * Linear polymers with periodic structure, low branching and stereoregularity (e. g. not atactic) have a semi-crystalline structure in the solid state. In simple polymers (such as polyethylene), the chains are present in the crystal in zigzag conformation. Several zigzag conformations form dense chain packs, called crystallites or lamellae. The lamellae are much thinner than the polymers are long (often about 10 nm). Wolfgang Kaiser: ''Kunststoffchemie für Ingenieure.'' 3. Auflage, Carl Hanser, München 2011, S. 84. They are formed by more or less regular folding of one or more molecular chains. Amorphous structures exist between the lamellae. Individual molecules can lead to entanglements between the lamellae and can also be involved in the formation of two (or more) lamellae (chains than called tie molecules). Several lamellae form a superstructure, a spherulite, often with a diameter in the range of 0.05 to 1 mm. :The type and arrangement of (functional) residues of the repeat units effects or determines the crystallinity and strength of the secondary valence bonds. In isotactic polypropylene, the molecules form a helix. Like the zigzag conformation, such helices allow a dense chain packing. Particularly strong intermolecular interactions occur when the residues of the repeating units allow the formation of

hydrogen bond In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a ...

s, as in the case of ''p''-aramid. The formation of strong intramolecular associations may produce diverse folded states of single linear chains with distinct circuit topology. Crystallinity and superstructure are always dependent on the conditions of their formation, see also: crystallization of polymers. Compared to amorphous structures, semi-crystalline structures lead to a higher stiffness, density, melting temperature and higher resistance of a polymer. * Cross-linked polymers: Wide-meshed cross-linked polymers are

s and cannot be molten (unlike thermoplastics); heating cross-linked polymers only leads to decomposition. Thermoplastic elastomers, on the other hand, are reversibly "physically crosslinked" and can be molten. Block copolymers in which a hard segment of the polymer has a tendency to crystallize and a soft segment has an amorphous structure are one type of thermoplastic elastomers: the hard segments ensure wide-meshed, physical crosslinking.

Crystallinity

When applied to polymers, the term ''crystalline'' has a somewhat ambiguous usage. In some cases, the term ''crystalline'' finds identical usage to that used in conventional

crystallography Crystallography is the experimental science of determining the arrangement of atoms in crystalline solids. Crystallography is a fundamental subject in the fields of materials science and solid-state physics (condensed matter physics). The wor ...

. For example, the structure of a crystalline protein or polynucleotide, such as a sample prepared for x-ray crystallography, may be defined in terms of a conventional unit cell composed of one or more polymer molecules with cell dimensions of hundreds of angstroms or more. A synthetic polymer may be loosely described as crystalline if it contains regions of three-dimensional ordering on atomic (rather than macromolecular) length scales, usually arising from intramolecular folding or stacking of adjacent chains. Synthetic polymers may consist of both crystalline and amorphous regions; the degree of crystallinity may be expressed in terms of a weight fraction or volume fraction of crystalline material. Few synthetic polymers are entirely crystalline. The crystallinity of polymers is characterized by their degree of crystallinity, ranging from zero for a completely non-crystalline polymer to one for a theoretical completely crystalline polymer. Polymers with microcrystalline regions are generally tougher (can be bent more without breaking) and more impact-resistant than totally amorphous polymers. Polymers with a degree of crystallinity approaching zero or one will tend to be transparent, while polymers with intermediate degrees of crystallinity will tend to be opaque due to light scattering by crystalline or glassy regions. For many polymers, crystallinity may also be associated with decreased transparency.

Chain conformation

The space occupied by a polymer molecule is generally expressed in terms of radius of gyration, which is an average distance from the center of mass of the chain to the chain itself. Alternatively, it may be expressed in terms of

pervaded volume Pervaded volume is a measure of the size of a polymer chain in space. In particular, it is "the volume of solution spanned by the polymer chain". Scaling The pervaded volume V scales as the cube of the chain size V \approx R^3 R is some lengt ...

, which is the volume spanned by the polymer chain and scales with the cube of the radius of gyration. The simplest theoretical models for polymers in the molten, amorphous state are ideal chains.

Properties

Polymer properties depend of their structure and they are divided into classes according to their physical bases. Many physical and chemical properties describe how a polymer behaves as a continuous macroscopic material. They are classified as bulk properties, or intensive properties according to thermodynamics.

Mechanical properties

The bulk properties of a polymer are those most often of end-use interest. These are the properties that dictate how the polymer actually behaves on a macroscopic scale.

Tensile strength

The tensile strength of a material quantifies how much elongating stress the material will endure before failure. This is very important in applications that rely upon a polymer's physical strength or durability. For example, a rubber band with a higher tensile strength will hold a greater weight before snapping. In general, tensile strength increases with polymer chain length and crosslinking of polymer chains.

Young's modulus of elasticity

Young's modulus quantifies the

elasticity Elasticity often refers to: *Elasticity (physics), continuum mechanics of bodies that deform reversibly under stress Elasticity may also refer to: Information technology * Elasticity (data store), the flexibility of the data model and the cl ...

of the polymer. It is defined, for small strains, as the ratio of rate of change of stress to strain. Like tensile strength, this is highly relevant in polymer applications involving the physical properties of polymers, such as rubber bands. The modulus is strongly dependent on temperature. Viscoelasticity describes a complex time-dependent elastic response, which will exhibit

hysteresis Hysteresis is the dependence of the state of a system on its history. For example, a magnet may have more than one possible magnetic moment in a given magnetic field, depending on how the field changed in the past. Plots of a single component of ...

in the stress-strain curve when the load is removed. Dynamic mechanical analysis or DMA measures this complex modulus by oscillating the load and measuring the resulting strain as a function of time.

Transport properties

Transport properties Transport (in British English), or transportation (in American English), is the intentional movement of humans, animals, and goods from one location to another. Modes of transport include air, land ( rail and road), water, cable, pip ...

such as diffusivity describe how rapidly molecules move through the polymer matrix. These are very important in many applications of polymers for films and membranes. The movement of individual macromolecules occurs by a process called reptation in which each chain molecule is constrained by entanglements with neighboring chains to move within a virtual tube. The theory of reptation can explain polymer molecule dynamics and viscoelasticity.

Phase behavior

Crystallization and melting

Depending on their chemical structures, polymers may be either semi-crystalline or amorphous. Semi-crystalline polymers can undergo crystallization and melting transitions, whereas amorphous polymers do not. In polymers, crystallization and melting do not suggest solid-liquid phase transitions, as in the case of water or other molecular fluids. Instead, crystallization and melting refer to the phase transitions between two solid states (''i.e.'', semi-crystalline and amorphous). Crystallization occurs above the glass-transition temperature (''T''_g) and below the melting temperature (''T''_m).

Glass transition

All polymers (amorphous or semi-crystalline) go through

s. The glass-transition temperature (''T''_g) is a crucial physical parameter for polymer manufacturing, processing, and use. Below ''T''_g, molecular motions are frozen and polymers are brittle and glassy. Above ''T''_g, molecular motions are activated and polymers are rubbery and viscous. The glass-transition temperature may be engineered by altering the degree of branching or crosslinking in the polymer or by the addition of plasticizers. Whereas crystallization and melting are first-order phase transitions, the glass transition is not. The glass transition shares features of second-order phase transitions (such as discontinuity in the heat capacity, as shown in the figure), but it is generally not considered a thermodynamic transition between equilibrium states.

Mixing behavior

In general, polymeric mixtures are far less

miscible Miscibility () is the property of two substances to mix in all proportions (that is, to fully dissolve in each other at any concentration), forming a homogeneous mixture (a solution). The term is most often applied to liquids but also applies ...

than mixtures of small molecule materials. This effect results from the fact that the driving force for mixing is usually entropy, not interaction energy. In other words, miscible materials usually form a solution not because their interaction with each other is more favorable than their self-interaction, but because of an increase in entropy and hence free energy associated with increasing the amount of volume available to each component. This increase in entropy scales with the number of particles (or moles) being mixed. Since polymeric molecules are much larger and hence generally have much higher specific volumes than small molecules, the number of molecules involved in a polymeric mixture is far smaller than the number in a small molecule mixture of equal volume. The energetics of mixing, on the other hand, is comparable on a per volume basis for polymeric and small molecule mixtures. This tends to increase the free energy of mixing for polymer solutions and thereby making solvation less favorable, and thereby making the availability of concentrated solutions of polymers far rarer than those of small molecules. Furthermore, the phase behavior of polymer solutions and mixtures is more complex than that of small molecule mixtures. Whereas most small molecule solutions exhibit only an upper critical solution temperature phase transition (UCST), at which phase separation occurs with cooling, polymer mixtures commonly exhibit a lower critical solution temperature phase transition (LCST), at which phase separation occurs with heating. In dilute solutions, the properties of the polymer are characterized by the interaction between the solvent and the polymer. In a good solvent, the polymer appears swollen and occupies a large volume. In this scenario, intermolecular forces between the solvent and monomer subunits dominate over intramolecular interactions. In a bad solvent or poor solvent, intramolecular forces dominate and the chain contracts. In the theta solvent, or the state of the polymer solution where the value of the second virial coefficient becomes 0, the intermolecular polymer-solvent repulsion balances exactly the intramolecular monomer-monomer attraction. Under the theta condition (also called the Flory condition), the polymer behaves like an ideal random coil. The transition between the states is known as a coil–globule transition.

Inclusion of plasticizers

Inclusion of plasticizers tends to lower T_g and increase polymer flexibility. Addition of the plasticizer will also modify dependence of the glass-transition temperature T_g on the cooling rate. The mobility of the chain can further change if the molecules of plasticizer give rise to hydrogen bonding formation. Plasticizers are generally small molecules that are chemically similar to the polymer and create gaps between polymer chains for greater mobility and fewer interchain interactions. A good example of the action of plasticizers is related to polyvinylchlorides or PVCs. A uPVC, or unplasticized polyvinylchloride, is used for things such as pipes. A pipe has no plasticizers in it, because it needs to remain strong and heat-resistant. Plasticized PVC is used in clothing for a flexible quality. Plasticizers are also put in some types of cling film to make the polymer more flexible.

Chemical properties

The attractive forces between polymer chains play a large part in determining the polymer’s properties. Because polymer chains are so long, they have many such interchain interactions per molecule, amplifying the effect of these interactions on the polymer properties in comparison to attractions between conventional molecules. Different side groups on the polymer can lend the polymer to ionic bonding or hydrogen bonding between its own chains. These stronger forces typically result in higher tensile strength and higher crystalline melting points. The intermolecular forces in polymers can be affected by dipoles in the monomer units. Polymers containing amide or carbonyl groups can form

s between adjacent chains; the partially positively charged hydrogen atoms in N-H groups of one chain are strongly attracted to the partially negatively charged oxygen atoms in C=O groups on another. These strong hydrogen bonds, for example, result in the high tensile strength and melting point of polymers containing

urethane Urethane may refer to: * Ethyl carbamate, a chemical compound which is an ester of carbamic acid * Polyurethane, a polymer composed of a chain of organic units joined by carbamate (urethane) links *Carbamate In organic chemistry, a carbamate is ...

or urea linkages.

Polyester Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include natural ...

s have dipole-dipole bonding between the oxygen atoms in C=O groups and the hydrogen atoms in H-C groups. Dipole bonding is not as strong as hydrogen bonding, so a polyester's melting point and strength are lower than Kevlar's ( Twaron), but polyesters have greater flexibility. Polymers with non-polar units such as polyethylene interact only through weak Van der Waals forces. As a result, they typically have lower melting temperatures than other polymers. When a polymer is dispersed or dissolved in a liquid, such as in commercial products like paints and glues, the chemical properties and molecular interactions influence how the solution flows and can even lead to self-assembly of the polymer into complex structures. When a polymer is applied as a coating, the chemical properties will influence the adhesion of the coating and how it interacts with external materials, such as superhydrophobic polymer coatings leading to water resistance. Overall the chemical properties of a polymer are important elements for designing new polymeric material products.

Optical properties

Polymers such as PMMA and HEMA:MMA are used as matrices in the gain medium of solid-state dye lasers, also known as solid-state dye-doped polymer lasers. These polymers have a high surface quality and are also highly transparent so that the laser properties are dominated by the laser dye used to dope the polymer matrix. These type of lasers, that also belong to the class of organic lasers, are known to yield very narrow linewidths which is useful for spectroscopy and analytical applications. An important optical parameter in the polymer used in laser applications is the change in refractive index with temperature also known as dn/dT. For the polymers mentioned here the (dn/dT) ~ −1.4 × 10⁻⁴ in units of K⁻¹ in the 297 ≤ T ≤ 337 K range.

Electrical properties

Most conventional polymers such as polyethylene are

electrical insulators An electrical insulator is a material in which electric current does not flow freely. The atoms of the insulator have tightly bound electrons which cannot readily move. Other materials—semiconductors and conductors—conduct electric current ...

, but the development of polymers containing π-conjugated bonds has led to a wealth of polymer-based semiconductors, such as polythiophenes. This has led to many applications in the field of organic electronics.

Applications

Nowadays, synthetic polymers are used in almost all walks of life. Modern society would look very different without them. The spreading of polymer use is connected to their unique properties: low density, low cost, good thermal/electrical insulation properties, high resistance to corrosion, low-energy demanding polymer manufacture and facile processing into final products. For a given application, the properties of a polymer can be tuned or enhanced by combination with other materials, as in composites. Their application allows to save energy (lighter cars and planes, thermally insulated buildings), protect food and drinking water (packaging), save land and lower use of fertilizers (synthetic fibres), preserve other materials (coatings), protect and save lifes (hygiene, medical applications). A representative, non-exhaustive list of applications is given below. * Clothing, sportswear and accessories:

polyester Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include natural ...

and PVC clothing, spandex, sport shoes, wetsuits,

footballs A football is a ball inflated with air that is used to play one of the various sports known as football. In these games, with some exceptions, goals or points are scored only when the ball enters one of two designated goal-scoring areas; football ...

and billiard balls, skis and

snowboard Snowboards are boards where the user places both feet, usually secured, to the same board. The board itself is wider than most skis, with the ability to glide on snow."snowboarding." Dictionary.com Unabridged (v 1.1). Random House, Inc. 17 Mar ...

s, rackets,

parachute A parachute is a device used to slow the motion of an object through an atmosphere by creating drag or, in a ram-air parachute, aerodynamic lift. A major application is to support people, for recreation or as a safety device for aviators, who ...

sail A sail is a tensile structure—which is made from fabric or other membrane materials—that uses wind power to propel sailing craft, including sailing ships, sailboats, windsurfers, ice boats, and even sail-powered land vehicles. Sails may ...

s, tents and shelters. * Electronic and photonic technologies: organic field effect transistors (OFET), light emitting diodes (OLED) and solar cells, television components, compact discs (CD), photoresists, holography. * Packaging and containers:

films A film also called a movie, motion picture, moving picture, picture, photoplay or (slang) flick is a work of visual art that simulates experiences and otherwise communicates ideas, stories, perceptions, feelings, beauty, or atmosphere ...

, bottles, food packaging,

barrel A barrel or cask is a hollow cylindrical container with a bulging center, longer than it is wide. They are traditionally made of wooden staves and bound by wooden or metal hoops. The word vat is often used for large containers for liquids, ...

s. * Insulation: electrical and thermal insulation, spray foams. * Construction and structural applications: garden furniture, PVC windows, flooring, sealing, pipes. * Paints, glues and lubricants:

varnish Varnish is a clear transparent hard protective coating or film. It is not a stain. It usually has a yellowish shade from the manufacturing process and materials used, but it may also be pigmented as desired, and is sold commercially in various ...

adhesive Adhesive, also known as glue, cement, mucilage, or paste, is any non-metallic substance applied to one or both surfaces of two separate items that binds them together and resists their separation. The use of adhesives offers certain advant ...

s, dispersants, anti-graffiti coatings, antifouling coatings, non-stick surfaces,

lubricant A lubricant (sometimes shortened to lube) is a substance that helps to reduce friction between surfaces in mutual contact, which ultimately reduces the heat generated when the surfaces move. It may also have the function of transmitting forces, t ...

s. * Car parts: tires, bumpers, windshields, windscreen wipers, fuel tanks, car seats. * Household items: buckets, kitchenware, toys (e.g., construction sets and

Rubik's cube The Rubik's Cube is a Three-dimensional space, 3-D combination puzzle originally invented in 1974 by Hungarians, Hungarian sculptor and professor of architecture Ernő Rubik. Originally called the Magic Cube, the puzzle was licensed by Rubik t ...

). * Medical applications:

blood bag Whole blood (WB) is human blood from a standard blood donation. It is used in the treatment of massive bleeding, in exchange transfusion, and when people donate blood to themselves. One unit of whole blood (~517 mls) brings up hemoglobin level ...

syringe A syringe is a simple reciprocating pump consisting of a plunger (though in modern syringes, it is actually a piston) that fits tightly within a cylindrical tube called a barrel. The plunger can be linearly pulled and pushed along the inside ...

s, rubber gloves,

surgical suture A surgical suture, also known as a stitch or stitches, is a medical device used to hold body tissues together and approximate wound edges after an injury or surgery. Application generally involves using a needle with an attached length of threa ...

contact lens Contact lenses, or simply contacts, are thin lenses placed directly on the surface of the eyes. Contact lenses are ocular prosthetic devices used by over 150 million people worldwide, and they can be worn to correct vision or for cosmetic ...

es,

prosthesis In medicine, a prosthesis (plural: prostheses; from grc, πρόσθεσις, prósthesis, addition, application, attachment), or a prosthetic implant, is an artificial device that replaces a missing body part, which may be lost through trau ...

, controlled drug delivery and release, matrices for cell growth. * Personal hygiene and healthcare:

diaper A diaper /ˈdaɪpə(r)/ (American and Canadian English) or a nappy ( Australian English, British English, and Hiberno-English) is a type of underwear that allows the wearer to urinate or defecate Defecation (or defaecation) follows dig ...

s using

superabsorbent polymer A superabsorbent polymer (SAP) (also called slush powder) is a water-absorbing hydrophilic homopolymers or copolymers that can absorb and retain extremely large amounts of a liquid relative to its own mass. Water-absorbing polymers, which are cla ...

s, toothbrushes, cosmetics, shampoo,

condom A condom is a sheath-shaped barrier device used during sexual intercourse to reduce the probability of pregnancy or a sexually transmitted infection (STI). There are both male and female condoms. With proper use—and use at every act of in ...

s. * Security: personal protective equipment,

bulletproof vest A bulletproof vest, also known as a ballistic vest or a bullet-resistant vest, is an item of body armor that helps absorb the impact and reduce or stop penetration to the torso from firearm-fired projectiles and fragmentation from explosions. T ...

s, space suits, ropes. * Separation technologies: synthetic membranes, fuel cell membranes,

filtration Filtration is a physical separation process that separates solid matter and fluid from a mixture using a ''filter medium'' that has a complex structure through which only the fluid can pass. Solid particles that cannot pass through the filter ...

, ion-exchange resins. * Money: polymer banknotes and payment cards. *

3D printing 3D printing or additive manufacturing is the Manufacturing, construction of a three-dimensional object from a computer-aided design, CAD model or a digital 3D modeling, 3D model. It can be done in a variety of processes in which material is ...

Standardized nomenclature

There are multiple conventions for naming polymer substances. Many commonly used polymers, such as those found in consumer products, are referred to by a common or trivial name. The trivial name is assigned based on historical precedent or popular usage rather than a standardized naming convention. Both the American Chemical Society (ACS) and IUPAC have proposed standardized naming conventions; the ACS and IUPAC conventions are similar but not identical. Examples of the differences between the various naming conventions are given in the table below: In both standardized conventions, the polymers' names are intended to reflect the monomer(s) from which they are synthesized (source based nomenclature) rather than the precise nature of the repeating subunit. For example, the polymer synthesized from the simple alkene ethene is called polyethene, retaining the ''-ene'' suffix even though the double bond is removed during the polymerization process: :→ :However, IUPAC structure based nomenclature is based on naming of the preferred constitutional repeating unit.

Characterization

Polymer characterization spans many techniques for determining the chemical composition, molecular weight distribution, and physical properties. Select common techniques include the following: * Size-exclusion chromatography (also called gel permeation chromatography), sometimes coupled with static light scattering, can used to determine the number-average molecular weight, weight-average molecular weight, and dispersity. *Scattering techniques, such as static light scattering and small-angle neutron scattering, are used to determine the dimensions ( radius of gyration) of macromolecules in solution or in the melt. These techniques are also used to characterize the three-dimensional structure of microphase-separated

block polymer In polymer chemistry, a copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained from the copolymerization of two monomer species are some ...

s, polymeric micelles, and other materials. * Wide-angle X-ray scattering (also called wide-angle X-ray diffraction) is used to determine the crystalline structure of polymers (or lack thereof). *Spectroscopy techniques, including Fourier-transform infrared spectroscopy,

Raman spectroscopy Raman spectroscopy () (named after Indian physicist C. V. Raman) is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman sp ...

, and nuclear magnetic resonance spectroscopy, can be used to determine the chemical composition. *

Differential scanning calorimetry Differential scanning calorimetry (DSC) is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and ref ...

is used to characterize the thermal properties of polymers, such as the glass-transition temperature, crystallization temperature, and melting temperature. The glass-transition temperature can also be determined by dynamic mechanical analysis. * Thermogravimetry is a useful technique to evaluate the thermal stability of the polymer. * Rheology is used to characterize the flow and deformation behavior. It can be used to determine the viscosity, modulus, and other rheological properties. Rheology is also often used to determine the molecular architecture (molecular weight, molecular weight distribution, branching) and to understand how the polymer can be processed.

Degradation

Polymer degradation is a change in the properties—tensile strength, color, shape, or molecular weight—of a polymer or polymer-based product under the influence of one or more environmental factors, such as heat, light, and the presence of certain chemicals, oxygen, and

enzymes Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrate (chemistry), substrates, and the enzyme converts the substrates into different molecule ...

. This change in properties is often the result of bond breaking in the polymer backbone ( chain scission) which may occur at the chain ends or at random positions in the chain. Although such changes are frequently undesirable, in some cases, such as biodegradation and recycling, they may be intended to prevent environmental pollution. Degradation can also be useful in biomedical settings. For example, a copolymer of

polylactic acid Polylactic acid, also known as poly(lactic acid) or polylactide (PLA), is a thermoplastic polyester with backbone formula or , formally obtained by condensation of lactic acid with loss of water (hence its name). It can also be prepared by rin ...

and polyglycolic acid is employed in hydrolysable stitches that slowly degrade after they are applied to a wound. The susceptibility of a polymer to degradation depends on its structure. Epoxies and chains containing aromatic functionalities are especially susceptible to UV degradation while polyesters are susceptible to degradation by hydrolysis. Polymers containing an unsaturated backbone degrade via ozone cracking. Carbon based polymers are more susceptible to thermal degradation than inorganic polymers such as polydimethylsiloxane and are therefore not ideal for most high-temperature applications. The degradation of polyethylene occurs by random scission—a random breakage of the bonds that hold the atoms of the polymer together. When heated above 450 °C, polyethylene degrades to form a mixture of hydrocarbons. In the case of chain-end scission, monomers are released and this process is referred to as unzipping or depolymerization. Which mechanism dominates will depend on the type of polymer and temperature; in general, polymers with no or a single small substituent in the repeat unit will decompose via random-chain scission. The sorting of polymer waste for recycling purposes may be facilitated by the use of the resin identification codes developed by the Society of the Plastics Industry to identify the type of plastic.

Product failure

Failure of safety-critical polymer components can cause serious accidents, such as fire in the case of cracked and degraded polymer fuel lines. Chlorine-induced cracking of acetal resin plumbing joints and polybutylene pipes has caused many serious floods in domestic properties, especially in the US in the 1990s. Traces of chlorine in the water supply attacked polymers present in the plumbing, a problem which occurs faster if any of the parts have been poorly extruded or injection molded. Attack of the acetal joint occurred because of faulty molding, leading to cracking along the threads of the fitting where there is

stress concentration In solid mechanics, a stress concentration (also called a stress raiser or a stress riser) is a location in an object where the stress is significantly greater than the surrounding region. Stress concentrations occur when there are irregularitie ...

. Polymer oxidation has caused accidents involving medical devices. One of the oldest known failure modes is ozone cracking caused by chain scission when ozone gas attacks susceptible

s, such as natural rubber and nitrile rubber. They possess double bonds in their repeat units which are cleaved during ozonolysis. Cracks in fuel lines can penetrate the bore of the tube and cause fuel leakage. If cracking occurs in the engine compartment, electric sparks can ignite the gasoline and can cause a serious fire. In medical use degradation of polymers can lead to changes of physical and chemical characteristics of implantable devices. Nylon 66 is susceptible to acid hydrolysis, and in one accident, a fractured fuel line led to a spillage of diesel into the road. If diesel fuel leaks onto the road, accidents to following cars can be caused by the slippery nature of the deposit, which is like black ice. Furthermore, the

asphalt concrete Asphalt concrete (commonly called asphalt, blacktop, or pavement in North America, and tarmac, bitumen macadam, or rolled asphalt in the United Kingdom and the Republic of Ireland) is a composite material commonly used to surface roads, parkin ...

road surface will suffer damage as a result of the diesel fuel dissolving the asphaltenes from the composite material, this resulting in the degradation of the asphalt surface and structural integrity of the road.

References

Bibliography

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External links

How to Analyze Polymers Using X-ray DiffractionPolymer Chemistry Hypertext, Educational resourceIntroduction to Polymers
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