Polymer

A polymer (/ˈpɒlɪmər/;[3][4] Greek poly-, "many" + -mer, "part") is a large molecule, or macromolecule, composed of many repeated subunits.[5] Due to their broad range of properties,[6] both synthetic and natural polymers play essential and ubiquitous roles in everyday life.[7] Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass relative to small molecule compounds produces unique physical properties, including toughness, viscoelasticity, and a tendency to form glasses and semicrystalline structures rather than crystals. The terms polymer and resin are often synonymous with plastic.

The term "polymer" derives from the Greek word πολύς (polus, meaning "many, much") and μέρος (meros, meaning "part"), and refers to a molecule whose structure is composed of multiple repeating units, from which originates a characteristic of high relative molecular mass and attendant properties.[2] The units composing polymers derive, actually or conceptually, from molecules of low relative molecular mass.[2] The term was coined in 1833 by Jöns Jacob Berzelius, though with a definition distinct from the modern IUPAC definition.[8][9] The modern concept of polymers as covalently bonded macromolecular structures was proposed in 1920 by Hermann Staudinger,[10] who spent the next decade finding experimental evidence for this hypothesis.[11]

Polymers are studied in the fields of biophysics and macromolecular science, and polymer science (which includes polymer chemistry and polymer physics). Historically, products arising from the linkage of repeating units by covalent chemical bonds have been the primary focus of polymer science; emerging important areas of the science now focus on non-covalent links. Polyisoprene of latex rubber is an example of a natural/biological polymer, and the polystyrene of styrofoam is an example of a synthetic polymer. In biological contexts, essentially all biological macromolecules—i.e., proteins (polyamides), nucleic acids (polynucleotides), and polysaccharides—are purely polymeric, or are composed in large part of polymeric components—e.g., isoprenylated/lipid-modified glycoproteins, where small lipidic molecules and oligosaccharide modifications occur on the polyamide backbone of the protein.[12]

The simplest theoretical models for polymers are ideal chains.

Single Polymer Chains AFM
Appearance of real linear polymer chains as recorded using an atomic force microscope on a surface, under liquid medium. Chain contour length for this polymer is ~204 nm; thickness is ~0.4 nm.[1]

Common examples

Polymers are of two types: naturally occurring and synthetic or man made.

Natural polymeric materials such as hemp, shellac, amber, wool, silk and natural rubber have been used for centuries. A variety of other natural polymers exist, such as cellulose, which is the main constituent of wood and paper.

The list of synthetic polymers, roughly in order of worldwide demand, includes polyethylene, polypropylene, polystyrene, polyvinyl chloride, synthetic rubber, phenol formaldehyde resin (or Bakelite), neoprene, nylon, polyacrylonitrile, PVB, silicone, and many more. More than 330 million tons of these polymers are made every year (2015).[13]

Most commonly, the continuously linked backbone of a polymer used for the preparation of plastics consists mainly of carbon atoms. A simple example is polyethylene ('polythene' in British English), whose repeating unit is based on ethylene monomer. Many other structures do exist; for example, elements such as silicon form familiar materials such as silicones, examples being Silly Putty and waterproof plumbing sealant. Oxygen is also commonly present in polymer backbones, such as those of polyethylene glycol, polysaccharides (in glycosidic bonds), and DNA (in phosphodiester bonds).

Synthesis

Polypropylene
The repeating unit of the polymer polypropylene

Polymerization is the process of combining many small molecules known as monomers into a covalently bonded chain or network. During the polymerization process, some chemical groups may be lost from each monomer. This happens in the polymerization of PET polyester. The monomers are terephthalic acid (HOOC—C6H4—COOH) and ethylene glycol (HO—CH2—CH2—OH) but the repeating unit is —OC—C6H4—COO—CH2—CH2—O—, which corresponds to the combination of the two monomers with the loss of two water molecules. The distinct piece of each monomer that is incorporated into the polymer is known as a repeat unit or monomer residue.

Laboratory synthetic methods are generally divided into two categories, step-growth polymerization and chain-growth polymerization.[14] The essential difference between the two is that in chain growth polymerization, monomers are added to the chain one at a time only,[15] such as in polyethylene, whereas in step-growth polymerization chains of monomers may combine with one another directly,[16] such as in polyester. Newer methods, such as plasma polymerization do not fit neatly into either category. Synthetic polymerization reactions may be carried out with or without a catalyst. Laboratory synthesis of biopolymers, especially of proteins, is an area of intensive research.

Biological synthesis

ADN animation
Microstructure of part of a DNA double helix biopolymer

There are three main classes of biopolymers: polysaccharides, polypeptides, and polynucleotides. In living cells, they may be synthesized by enzyme-mediated processes, such as the formation of DNA catalyzed by DNA polymerase. The synthesis of proteins involves multiple enzyme-mediated processes to transcribe genetic information from the DNA to RNA and subsequently translate that information to synthesize the specified protein from amino acids. The protein may be modified further following translation in order to provide appropriate structure and functioning. There are other biopolymers such as rubber, suberin, melanin and lignin.

Modification of natural polymers

Naturally occurring polymers such as cotton, starch and rubber were familiar materials for years before synthetic polymers such as polyethene and perspex appeared on the market. Many commercially important polymers are synthesized by chemical modification of naturally occurring polymers. Prominent examples include the reaction of nitric acid and cellulose to form nitrocellulose and the formation of vulcanized rubber by heating natural rubber in the presence of sulfur. Ways in which polymers can be modified include oxidation, cross-linking and endcapping.

Especially in the production of polymers the gas separation by membranes has acquired increasing importance in the petrochemical industry and is now a relatively well-established unit operation. The process of polymer degassing is necessary to suit polymer for extrusion and pelletizing, increasing safety, environmental, and product quality aspects. Nitrogen is generally used for this purpose, resulting in a vent gas primarily composed of monomers and nitrogen.[17]

Properties

Polymer properties are broadly divided into several classes based on the scale at which the property is defined as well as upon its physical basis.[18] The most basic property of a polymer is the identity of its constituent monomers. A second set of properties, known as microstructure, essentially describes the arrangement of these monomers within the polymer at the scale of a single chain. These basic structural properties play a major role in determining bulk physical properties of the polymer, which describe how the polymer behaves as a continuous macroscopic material. Chemical properties, at the nano-scale, describe how the chains interact through various physical forces. At the macro-scale, they describe how the bulk polymer interacts with other chemicals and solvents.

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. Polymers which contain only a single type of repeat unit are known as homopolymers, while polymers containing two or more types of repeat units are known as copolymers.[19] Terpolymers contain three types of repeat units.[20]

Poly(styrene) is composed only of styrene monomer residues, and is classified as a homopolymer. Ethylene-vinyl acetate 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 molecule containing ionizable subunits is known as a polyelectrolyte or ionomer.

Microstructure

The microstructure of a polymer (sometimes called configuration) relates to the physical arrangement of monomer residues along the backbone of the chain.[21] These are the elements of polymer structure that require the breaking of a covalent bond in order to change. Structure has a strong influence on the other properties of a polymer. For example, two samples of natural rubber may exhibit different durability, even though their molecules comprise the same monomers.

Polymer architecture

Polymer Branch
Branch point in a polymer

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.[22] A branched polymer molecule is composed of a main chain with one or more substituent side chains or branches. Types of branched polymers include star polymers, comb polymers, brush polymers, dendronized polymers, ladder polymers, and dendrimers.[22] There exist also two-dimensional polymers which are composed of topologically planar repeat units. A polymer's architecture affects many of its physical properties including, but not limited to, 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.[23][24] 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 (Mn) and weight-average molecular weight (Mw) are most commonly reported.[25][26] The ratio of these two values (Mw / Mn) is the dispersity (Đ), which is commonly used to express the width of the molecular weight distribution.[27]

The physical properties[28] of polymer strongly depend on the length (or equivalently, the molecular weight) of the polymer chain.[29] One important example of the physical consequences of the molecular weight is the scaling of the viscosity (resistance to flow) in the melt.[30] The influence of the weight-average molecular weight (Mw) on the melt viscosity (η) depends on whether the polymer is above or below the onset of entanglements. Below the entanglement molecular weight, , whereas above the entanglement molecular weight, . In the latter case, increasing the polymer chain length 10-fold would increase the viscosity over 1000 times.[31] Increasing chain length furthermore tends to decrease chain mobility, increase strength and toughness, and increase the glass transition temperature (Tg).[32] This is a result of the increase in chain interactions such as Van der Waals attractions and entanglements that come with increased chain length.[33][34] 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

Different types of copolymers

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.[35] Alternating, periodic and block copolymers are simple examples of sequence-controlled polymers.

  • Alternating copolymers possess two regularly alternating monomer residues:[36] [AB]n (structure 2 at right). An example is the equimolar copolymer of styrene and maleic anhydride formed by free-radical chain-growth polymerization.[37] 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.[38]
  • Periodic copolymers have monomer residue types arranged in a repeating sequence: [AnBm...] m being different from n.
  • 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[39][40] (structure 3). For example, the chain-growth copolymer of vinyl chloride and vinyl acetate is random.[37]
  • Block copolymers have long sequences of different monomer units[37][38] (structure 4). 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.[38] (structure 5) The branches are added on to a preformed main chain macromolecule.[37]

Tacticity

Tacticity describes the relative stereochemistry 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.

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. 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 and/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.[41] 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.[42] 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, reduced crystallinity may also be associated with increased 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, which is the volume of solution spanned by the polymer chain and scales with the cube of the radius of gyration.[43]

Mechanical properties

Stable neck MDPE
A polyethylene sample that has necked under tension.

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.[44][45] 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 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 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 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.[46]

Phase behavior

Crystallization and melting

Thermal transitions in (A) amorphous and (B) semicrystalline polymers, represented as traces from differential scanning calorimetry. As the temperature increases, both amorphous and semicrystalline polymers go through the glass transition (Tg). Amorphous polymers (A) do not exhibit other phase transitions, though semicrystalline polymers (B) undergo crystallization and melting (at temperatures Tc and Tm, respectively).

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 (Tg) and below the melting temperature (Tm).

Glass transition

All polymers (amorphous or semi-crystalline) go through glass transitions. The glass transition temperature (Tg) is a crucial physical parameter for polymer manufacturing, processing, and use. Below Tg, molecular motions are frozen and polymers are brittle and glassy. Above Tg, 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.[47]

Whereas crystallization and melting are first-order phase transitions, the glass transition is not.[48] 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

LCST-UCST plot
Phase diagram of the typical mixing behavior of weakly interacting polymer solutions, showing spinodal curves and binodal coexistence curves.

In general, polymeric mixtures are far less miscible 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, at which phase separation occurs with cooling, polymer mixtures commonly exhibit a lower critical solution temperature phase transition, at which phase separation occurs with heating.

In dilute solution, 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 Tg and increase polymer flexibility. Plasticizers are generally small molecules that are chemically similar to the polymer and create gaps between polymer chains for greater mobility and reduced interchain interactions. A good example of the action of plasticizers is related to polyvinylchlorides or PVCs. An 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 polymer's properties. Because polymer chains are so long, these interchain forces are amplified far beyond the 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 hydrogen bonds 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 or urea linkages. Polyesters 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.

Ethene, however, has no permanent dipole. The attractive forces between polyethylene chains arise from weak Van der Waals forces. Molecules can be thought of as being surrounded by a cloud of negative electrons. As two polymer chains approach, their electron clouds repel one another. This has the effect of lowering the electron density on one side of a polymer chain, creating a slight positive dipole on this side. This charge is enough to attract the second polymer chain. Van der Waals forces are quite weak, however, so polyethylene can have a lower melting temperature compared to other polymers.

Optical properties

Polymers such as PMMA and HEMA:MMA are used as matrices in the gain medium of solid-state dye lasers that are also known as 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.[49] 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.[50]

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)[51] and IUPAC[52] have proposed standardized naming conventions; the ACS and IUPAC conventions are similar but not identical.[53] Examples of the differences between the various naming conventions are given in the table below:

Common name ACS name IUPAC name
Poly(ethylene oxide) or PEO Poly(oxyethylene) Poly(oxyethene)
Poly(ethylene terephthalate) or PET Poly(oxy-1,2-ethanediyloxycarbonyl-1,4-phenylenecarbonyl) Poly(oxyetheneoxyterephthaloyl)
Nylon 6 Poly[amino(1-oxo-1,6-hexanediyl)] Poly[amino(1-oxohexan-1,6-diyl)]

In both standardized conventions, the polymers' names are intended to reflect the monomer(s) from which they are synthesized rather than the precise nature of the repeating subunit. For example, the polymer synthesized from the simple alkene ethene is called polyethylene, retaining the -ene suffix even though the double bond is removed during the polymerization process:

Ethene polymerization
Polyethylene-repeat-2D-flat
Ethene polymerization
Polyethylene-repeat-2D-flat

Characterization

Polymer characterization spans many techniques for determining the chemical composition, molecular weight distribution, and physical properties. Select common techniques include the following:

Degradation

PlasticDamage
A plastic item with thirty years of exposure to heat and cold, brake fluid, and sunlight. Notice the discoloration, swelling, and crazing of the material

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, chemicals and, in some cases, galvanic action. It is often due to the scission of polymer chain bonds via hydrolysis, leading to a decrease in the molecular mass of the polymer.

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 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, while polymers containing an unsaturated backbone are especially susceptible to 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. High-temperature matrices such as bismaleimides (BMI), condensation polyimides (with an O-C-N bond), triazines (with a nitrogen (N) containing ring), and blends thereof are susceptible to polymer degradation in the form of galvanic corrosion when bare carbon fiber reinforced polymer CFRP is in contact with an active metal such as aluminium in salt water environments.

The degradation of polymers to form smaller molecules may proceed by random scission or specific scission. 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. Other polymers, such as poly(alpha-methylstyrene), undergo specific chain scission with breakage occurring only at the ends. They literally unzip or depolymerize back to the constituent monomer.

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

Chlorine attack1
Chlorine attack of acetal resin plumbing joint

In a finished product, such a change is to be prevented or delayed. 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 vulnerable polymers in the plastic 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 which is a serious stress concentration.

Ozone cracks in tube1
Ozone-induced cracking in natural rubber tubing

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 elastomers, 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.[54]

Fuel lines can also be attacked by another form of degradation: hydrolysis. Nylon 6,6 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 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.

See also

References

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External links

Bioplastic

Bioplastics are plastics derived from renewable biomass sources, such as vegetable fats and oils, corn starch, straw, woodchips, food waste, etc. Bioplastic can be made from agricultural by-products and also from used plastic bottles and other containers using microorganisms. Common plastics, such as fossil-fuel plastics (also called petrobased polymers) are derived from petroleum or natural gas. Not all bioplastics are biodegradable nor biodegrade more readily than commodity fossil-fuel derived plastics. Bioplastics are usually derived from sugar derivatives, including starch, cellulose, and lactic acid. As of 2014, bioplastics represented approximately 0.2% of the global polymer market (300 million tons).

Biopolymer

Biopolymers are polymers produced by living organisms; in other words, they are polymeric biomolecules. Biopolymers contain monomeric units that are covalently bonded to form larger structures. There are three main classes of biopolymers, classified according to the monomeric units used and the structure of the biopolymer formed: polynucleotides (RNA and DNA), which are long polymers composed of 13 or more nucleotide monomers; polypeptides, which are short polymers of amino acids; and polysaccharides, which are often linear bonded polymeric carbohydrate structures. Other examples of biopolymers include rubber, suberin, melanin and lignin.

Cellulose is the most common organic compound and biopolymer on Earth. About 33 percent of all plant matter is cellulose. The cellulose content of cotton is 90 percent, for wood it is 50 percent.

Carbon fiber reinforced polymer

Carbon fiber reinforced polymer, carbon fiber reinforced plastic, or carbon fiber reinforced thermoplastic (CFRP, CRP, CFRTP, or often simply carbon fiber, carbon composite, or even carbon), is an extremely strong and light fiber-reinforced plastic which contains carbon fibers. The alternative spelling 'fibre' is common in British Commonwealth countries. CFRPs can be expensive to produce but are commonly used wherever high strength-to-weight ratio and stiffness (rigidity) are required, such as aerospace, superstructure of ships, automotive, civil engineering, sports equipment, and an increasing number of consumer and technical applications.

The binding polymer is often a thermoset resin such as epoxy, but other thermoset or thermoplastic polymers, such as polyester, vinyl ester, or nylon, are sometimes used. The composite material may contain aramid (e.g. Kevlar, Twaron), ultra-high-molecular-weight polyethylene (UHMWPE), aluminium, or glass fibers in addition to carbon fibers. The properties of the final CFRP product can also be affected by the type of additives introduced to the binding matrix (resin). The most common additive is silica, but other additives such as rubber and carbon nanotubes can be used. The material is also referred to as graphite-reinforced polymer or graphite fiber-reinforced polymer (GFRP is less common, as it clashes with glass-(fiber)-reinforced polymer).

Conductive polymer

Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The biggest advantage of conductive polymers is their processability, mainly by dispersion. Conductive polymers are generally not thermoplastics, i.e., they are not thermoformable. But, like insulating polymers, they are organic materials. They can offer high electrical conductivity but do not show similar mechanical properties to other commercially available polymers. The electrical properties can be fine-tuned using the methods of organic synthesis and by advanced dispersion techniques.

Copolymer

A copolymer is a polymer derived from more than one species of monomer. The polymerization of monomers into copolymers is called copolymerization. Copolymers obtained by copolymerization of two monomer species are sometimes called bipolymers. Those obtained from three and four monomers are called terpolymers and quaterpolymers, respectively.

There are many commercially relevant copolymers. Some examples include acrylonitrile butadiene styrene (ABS), styrene/butadiene co-polymer (SBR), nitrile rubber, styrene-acrylonitrile, styrene-isoprene-styrene (SIS) and ethylene-vinyl acetate, all formed by chain-growth polymerization. Another production mechanism is step-growth polymerization, used to produce the nylon-12/6/66 copolymer of nylon 12, nylon 6 and nylon 66, as well as the copolyester family.

Since a copolymer consists of at least two types of constituent units (also structural units), copolymers can be classified based on how these units are arranged along the chain. Linear copolymers consist of a single main chain, and include alternating copolymers, statistical copolymers and block copolymers. Branched copolymers consist of a single main chain with one or more polymeric side chains, and can be grafted, star shaped or have other architectures.

Cross-link

In chemistry and biology a cross-link is a bond that links one polymer chain to another. These links may take the form of covalent bonds or ionic bonds and the polymers can be either synthetic polymers or natural polymers (such as proteins).

In polymer chemistry "cross-linking" usually refers to the use of cross-links to promote a change in the polymers' physical properties.

When "crosslinking" is used in the biological field, it refers to the use of a probe to link proteins together to check for protein–protein interactions, as well as other creative cross-linking methodologies.Although the term is used to refer to the "linking of polymer chains" for both sciences, the extent of crosslinking and specificities of the crosslinking agents vary greatly. As with all science, there are overlaps, and the following delineations are a starting point to understanding the subtleties.

Elastomer

An elastomer is a polymer with viscoelasticity (i.e., both viscosity and elasticity) and very weak intermolecular forces, and generally low Young's modulus and high failure strain compared with other materials. The term, a portmanteau of elastic polymer, is often used interchangeably with rubber, although the latter is preferred when referring to vulcanisates. Each of the monomers which link to form the polymer is usually a compound of several elements among carbon, hydrogen, oxygen and silicon. Elastomers are amorphous polymers maintained above their glass transition temperature, so that considerable molecular reconformation, without breaking of covalent bonds, is feasible. At ambient temperatures, such rubbers are thus relatively soft (E ≈ 3 MPa) and deformable. Their primary uses are for seals, adhesives and molded flexible parts. Application areas for different types of rubber are manifold and cover segments as diverse as tires, soles for shoes, and damping and insulating elements. The importance of these rubbers can be judged from the fact that global revenues are forecast to rise to US$56 billion in 2020.IUPAC defines the term "elastomer" by "Polymer that displays rubber-like elasticity."Manufacturers of Elastomeric parts include NoProto, PrintForm, 3D Systems, and Afformativ.

Rubber-like solids with elastic properties are called elastomers. Polymer chains are held together in these materials by relatively weak intermolecular bonds, which permit the polymers to stretch in response to macroscopic stresses. Natural rubber, neoprene rubber, buna-s and buna-n are all examples of such elastomers.

Electrolyte

An electrolyte is a substance that produces an electrically conducting solution when dissolved in a polar solvent, such as water. The dissolved electrolyte separates into cations and anions, which disperse uniformly through the solvent. Electrically, such a solution is neutral. If an electric potential is applied to such a solution, the cations of the solution are drawn to the electrode that has an abundance of electrons, while the anions are drawn to the electrode that has a deficit of electrons. The movement of anions and cations in opposite directions within the solution amounts to a current. This includes most soluble salts, acids, and bases. Some gases, such as hydrogen chloride, under conditions of high temperature or low pressure can also function as electrolytes. Electrolyte solutions can also result from the dissolution of some biological (e.g., DNA, polypeptides) and synthetic polymers (e.g., polystyrene sulfonate), termed "polyelectrolytes", which contain charged functional groups. A substance that dissociates into ions in solution acquires the capacity to conduct electricity. Sodium, potassium, chloride, calcium, magnesium, and phosphate are examples of electrolytes.

In medicine, electrolyte replacement is needed when a person has prolonged vomiting or diarrhea, and as a response to strenuous athletic activity. Commercial electrolyte solutions are available, particularly for sick children (such as oral rehydration solution, Suero Oral, or Pedialyte) and athletes (sports drinks). Electrolyte monitoring is important in the treatment of anorexia and bulimia.

Fiber

Fiber or fibre (see spelling differences, from the Latin fibra) is a natural or synthetic substance that is significantly longer than it is wide. Fibers are often used in the manufacture of other materials. The strongest engineering materials often incorporate fibers, for example carbon fiber and ultra-high-molecular-weight polyethylene.

Synthetic fibers can often be produced very cheaply and in large amounts compared to natural fibers, but for clothing natural fibers can give some benefits, such as comfort, over their synthetic counterparts.

Latex

Latex is a stable dispersion (emulsion) of polymer microparticles in an aqueous medium. It is found in nature, but synthetic latexes can be made by polymerizing a monomer such as styrene that has been emulsified with surfactants.

Latex as found in nature is a milky fluid found in 10% of all flowering plants (angiosperms). It is a complex emulsion consisting of proteins, alkaloids, starches, sugars, oils, tannins, resins, and gums that coagulate on exposure to air. It is usually exuded after tissue injury. In most plants, latex is white, but some have yellow, orange, or scarlet latex. Since the 17th century, latex has been used as a term for the fluid substance in plants. It serves mainly as defense against herbivorous insects. Latex is not to be confused with plant sap; it is a separate substance, separately produced, and with separate functions.

The word latex is also used to refer to natural latex rubber, particularly non-vulcanized rubber. Such is the case in products like latex gloves, latex condoms and latex clothing.

Originally, the name given to latex by indigenous Equator tribes who cultivated the plant was “caoutchouc”, from the words “caa” (tear) and “ochu” (tree), because of the way it is collected.

Lithium polymer battery

A lithium polymer battery, or more correctly lithium-ion polymer battery (abbreviated as LiPo, LIP, Li-poly, lithium-poly and others), is a rechargeable battery of lithium-ion technology using a polymer electrolyte instead of a liquid electrolyte. High conductivity semisolid (gel) polymers form this electrolyte. These batteries provide higher specific energy than other lithium battery types and are used in applications where weight is a critical feature, like mobile devices and radio-controlled aircraft.

OLED

An organic light-emitting diode (OLED) is a light-emitting diode (LED) in which the emissive electroluminescent layer is a film of organic compound that emits light in response to an electric current. This organic layer is situated between two electrodes; typically, at least one of these electrodes is transparent. OLEDs are used to create digital displays in devices such as television screens, computer monitors, portable systems such as smartphones, handheld game consoles and PDAs. A major area of research is the development of white OLED devices for use in solid-state lighting applications.There are two main families of OLED: those based on small molecules and those employing polymers. Adding mobile ions to an OLED creates a light-emitting electrochemical cell (LEC) which has a slightly different mode of operation. An OLED display can be driven with a passive-matrix (PMOLED) or active-matrix (AMOLED) control scheme. In the PMOLED scheme, each row (and line) in the display is controlled sequentially, one by one, whereas AMOLED control uses a thin-film transistor backplane to directly access and switch each individual pixel on or off, allowing for higher resolution and larger display sizes.

An OLED display works without a backlight because it emits visible light. Thus, it can display deep black levels and can be thinner and lighter than a liquid crystal display (LCD). In low ambient light conditions (such as a dark room), an OLED screen can achieve a higher contrast ratio than an LCD, regardless of whether the LCD uses cold cathode fluorescent lamps or an LED backlight.

Plastic

Plastic is material consisting of any of a wide range of synthetic or semi-synthetic organic compounds that are malleable and so can be molded into solid objects.

Plasticity is the general property of all materials which can deform irreversibly without breaking but, in the class of moldable polymers, this occurs to such a degree that their actual name derives from this specific ability.

Plastics are typically organic polymers of high molecular mass and often contain other substances. They are usually synthetic, most commonly derived from petrochemicals, however, an array of variants are made from renewable materials such as polylactic acid from corn or cellulosics from cotton linters.Due to their low cost, ease of manufacture, versatility, and imperviousness to water, plastics are used in a multitude of products of different scale, including paper clips and spacecraft. They have prevailed over traditional materials, such as wood, stone, horn and bone, leather, metal, glass, and ceramic, in some products previously left to natural materials.

In developed economies, about a third of plastic is used in packaging and roughly the same in buildings in applications such as piping, plumbing or vinyl siding. Other uses include automobiles (up to 20% plastic), furniture, and toys. In the developing world, the applications of plastic may differ—42% of India's consumption is used in packaging.Plastics have many uses in the medical field as well, with the introduction of polymer implants and other medical devices derived at least partially from plastic. The field of plastic surgery is not named for use of plastic materials, but rather the meaning of the word plasticity, with regard to the reshaping of flesh.

The world's first fully synthetic plastic was bakelite, invented in New York in 1907 by Leo Baekeland who coined the term 'plastics'. Many chemists have contributed to the materials science of plastics, including Nobel laureate Hermann Staudinger who has been called "the father of polymer chemistry" and Herman Mark, known as "the father of polymer physics".The success and dominance of plastics starting in the early 20th century led to environmental concerns regarding its slow decomposition rate after being discarded as trash due to its composition of large molecules. Toward the end of the century, one approach to this problem was met with wide efforts toward recycling.

Polylactic acid

Poly(lactic acid) or polylactic acid or polylactide (PLA) is a biodegradable and bioactive thermoplastic aliphatic polyester derived from renewable biomass, typically from fermented plant starch such as from corn, cassava, sugarcane or sugar beet pulp. In 2010, PLA had the second highest consumption volume of any bioplastic of the world.The name "polylactic acid" does not comply with IUPAC standard nomenclature, and is potentially ambiguous or confusing, because PLA is not a polyacid (polyelectrolyte), but rather a polyester.

Polymer chemistry

Polymer chemistry is a sub-discipline of chemistry that focuses on the chemical synthesis, structure, chemical and physical properties of polymers and macromolecules. The principles and methods used within polymer chemistry are also applicable through a wide range of other chemistry sub-disciplines like organic chemistry, analytical chemistry, and physical chemistry Many materials have polymeric structures, from fully inorganic metals and ceramics to DNA and other biological molecules, however, polymer chemistry is typically referred to in the context of synthetic, organic compositions. Synthetic polymers are ubiquitous in commercial materials and products in everyday use, commonly referred to as plastics, and rubbers, and are major components of composite materials. Polymer chemistry can also be included in the broader fields of polymer science or even nanotechnology, both of which can be described as encompassing polymer physics and polymer engineering.

Polymerization

In polymer chemistry, polymerization is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many forms of polymerization and different systems exist to categorize them.

Polypropylene

Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. It is produced via chain-growth polymerization from the monomer propylene.

Polypropylene belongs to the group of polyolefins and is partially crystalline and non-polar. Its properties are similar to polyethylene, but it is slightly harder and more heat resistant. It is a white, mechanically rugged material and has a high chemical resistance. Polypropylene is the second-most widely produced commodity plastic (after polyethylene) and it is often used in packaging and labeling. In 2013, the global market for polypropylene was about 55 million tonnes.

Thermoplastic

A thermoplastic, or thermosoftening plastic, is a plastic polymer material that becomes pliable or moldable at a certain elevated temperature and solidifies upon cooling.Most thermoplastics have a high molecular weight. The polymer chains associate by intermolecular forces, which weaken rapidly with increased temperature, yielding a viscous liquid. In this state, thermoplastics may be reshaped and are typically used to produce parts by various polymer processing techniques such as injection molding, compression molding, calendering, and extrusion. Thermoplastics differ from thermosetting polymers which form irreversible chemical bonds during the curing process. Thermosets do not melt when heated, but typically decompose and do not reform upon cooling.

Above its glass transition temperature and below its melting point, the physical properties of a thermoplastic change drastically without an associated phase change. Some thermoplastics do not fully crystallize below the glass transition temperature, retaining some or all of their amorphous characteristics. Amorphous and semi-amorphous plastics are used when high optical clarity is necessary, as light is scattered strongly by crystallites larger than its wavelength. Amorphous and semi-amorphous plastics are less resistant to chemical attack and environmental stress cracking because they lack a crystalline structure.

Brittleness can be decreased with the addition of plasticizers, which increases the mobility of amorphous chain segments to effectively lower the glass transition temperature. Modification of the polymer through copolymerization or through the addition of non-reactive side chains to monomers before polymerization can also lower it. Before these techniques were employed, plastic automobile parts would often crack when exposed to cold temperatures.These are linear or slightly branched long chain molecules capable of repeatedly softening on heating and hardening on cooling.

Thermosetting polymer

A thermosetting polymer, resin, or plastic, often called a thermoset, is a polymer that is irreversibly hardened by curing from a soft solid or viscous liquid prepolymer or resin. Curing is induced by heat or suitable radiation and may be promoted by high pressure, or mixing with a catalyst. It results in chemical reactions that create extensive cross-linking between polymer chains to produce an infusible and insoluble polymer network.

The starting material for making thermosets is usually malleable or liquid prior to curing, and is often designed to be molded into the final shape. It may also be used as an adhesive. Once hardened, a thermoset cannot be melted for reshaping, in contrast to thermoplastic polymers which are commonly produced and distributed in form of pellets, and shaped into the final product form by melting, pressing, or injection molding.

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