Polymer (updated)

From Wikipedia, the free encyclopedia

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.

 

Polymer is a substance composed of macromolecules (synonym: polymer molecules).

 

Macromolecule = A molecule of high relative molecular mass, the structure of which essentially comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.

 

A polymer (/ˈpɒlɪmər/; Greek poly-, "many" + -mer, "part") is a large molecule, or macromolecule, composed of many repeated subunits. Due to their broad range of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. 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. The units composing polymers derive, actually or conceptually, from molecules of low relative molecular mass. The term was coined in 1833 by Jöns Jacob Berzelius, though with a definition distinct from the modern IUPAC definition. The modern concept of polymers as covalently bonded macromolecular structures was proposed in 1920 by Hermann Staudinger, who spent the next decade finding experimental evidence for this hypothesis.

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.

The simplest theoretical models for polymers are ideal chains.

Common examples

Polymers are of two types: naturally occurring and synthetic or man made.  (DJS:  I would say free-radical and condensation.)

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).

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. However, 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

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 is the case, for example, 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. The essential difference between the two is that in chain growth polymerization, monomers are added to the chain one at a time only, such as in polyethylene, whereas in step-growth polymerization chains of monomers may combine with one another directly, such as in polyester. However, some 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

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.

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. 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 that 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. Terpolymers contain three types of repeat units.

Poly(styrene), for example, is composed only of styrene monomer residues, and is therefore classified as a homopolymer. Ethylene-vinyl acetate, on the other hand, contains more than one variety of repeat unit and is thus 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. 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

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. 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. 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. 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 (M_n) and weight-average molecular weight (M_w) are most commonly reported. 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. 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 (η) depends on whether the polymer is above or below the onset of entanglements. Below the entanglement molecular weight, ${\displaystyle \eta \,\sim {M_{w}}^{1}}$, whereas above the entanglement molecular weight, ${\displaystyle \eta \,\sim {M_{w}}^{3.4}}$. 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

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.

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

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. 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. Thus 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.

Mechanical properties

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. 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 relate to how rapidly molecules move through the polymer matrix. These are very important in many applications of polymers for films and membranes.

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 (T_g). Amorphous polymers (A) do not exhibit other phase transitions. However, semicrystalline polymers (B) undergo crystallization and melting (at temperatures T_c and T_m, 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 (T_g) and below the melting temperature (T_m).

Glass transition

All polymers (amorphous or semi-crystalline) go through glass transitions. 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

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 thus make solvation less favorable. Thus, concentrated solutions of polymers are 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 T_g 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. 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.

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:

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: 

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 polymers, 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, and nuclear magnetic resonance spectroscopy, can be used to determine the chemical composition.
• Differential scanning calorimetry 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

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 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-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.

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.

Methane clathrate (updated)

From Wikipedia, the free encyclopedia

"Burning ice". Methane, released by heating, burns; water drips.
Inset: clathrate structure (University of Göttingen, GZG. Abt. Kristallographie).
Source: United States Geological Survey.

 

Methane clathrate (CH₄·5.75H₂O) or (4CH₄·23H₂O), also called methane hydrate, hydromethane, methane ice, fire ice, natural gas hydrate, or gas hydrate, is a solid clathrate compound (more specifically, a clathrate hydrate) in which a large amount of methane is trapped within a crystal structure of water, forming a solid similar to ice. Originally thought to occur only in the outer regions of the Solar System, where temperatures are low and water ice is common, significant deposits of methane clathrate have been found under sediments on the ocean floors of the Earth.

Methane clathrates are common constituents of the shallow marine geosphere and they occur in deep sedimentary structures and form outcrops on the ocean floor. Methane hydrates are believed to form by the precipitation or crystallization of methane migrating from deep along geological faults. Precipitation occurs when the methane comes in contact with water within the sea bed subject to temperature and pressure. In 2008, research on Antarctic Vostok and EPICA Dome C ice cores revealed that methane clathrates were also present in deep Antarctic ice cores and record a history of atmospheric methane concentrations, dating to 800,000 years ago. The ice-core methane clathrate record is a primary source of data for global warming research, along with oxygen and carbon dioxide.

General

Methane hydrates were discovered in Russia in the 1960s, and studies for extracting gas from it emerged at the beginning of the 21st century.

Structure and composition

The nominal methane clathrate hydrate composition is (CH₄)₄(H₂O)₂₃, or 1 mole of methane for every 5.75 moles of water, corresponding to 13.4% methane by mass, although the actual composition is dependent on how many methane molecules fit into the various cage structures of the water lattice. The observed density is around 0.9 g/cm³, which means that methane hydrate will float to the surface of the sea or of a lake unless it is bound in place by being formed in or anchored to sediment. One liter of fully saturated methane clathrate solid would therefore contain about 120 grams of methane (or around 169 liters of methane gas at 0 °C and 1 atm), or one cubic metre of methane clathrate releases about 160 cubic metres of gas.

Methane forms a structure I hydrate with two dodecahedral (12 vertices, thus 12 water molecules) and six tetradecahedral (14 water molecules) water cages per unit cell. (Because of sharing of water molecules between cages, there are only 46 water molecules per unit cell.) This compares with a hydration number of 20 for methane in aqueous solution. A methane clathrate MAS NMR spectrum recorded at 275 K and 3.1 MPa shows a peak for each cage type and a separate peak for gas phase methane. In 2003, a clay-methane hydrate intercalate was synthesized in which a methane hydrate complex was introduced at the interlayer of a sodium-rich montmorillonite clay. The upper temperature stability of this phase is similar to that of structure I hydrate.

Methane hydrate phase diagram. The horizontal axis shows temperature from -15 to 33 Celsius, the vertical axis shows pressure from 0 to 120,000 kilopascals (0 to 1,184 atmospheres). Hydrate forms above the line. For example, at 4 Celsius hydrate forms above a pressure of about 50 atm/5000 kPa, found at about 500m sea depth.

Natural deposits

Worldwide distribution of confirmed or inferred offshore gas hydrate-bearing sediments, 1996. Source: USGS

 

Gas hydrate-bearing sediment, from the subduction zone off Oregon

 

Specific structure of a gas hydrate piece, from the subduction zone off Oregon

 

Methane clathrates are restricted to the shallow lithosphere (i.e. < 2,000 m depth). Furthermore, necessary conditions are found only in either continental sedimentary rocks in polar regions where average surface temperatures are less than 0 °C; or in oceanic sediment at water depths greater than 300 m where the bottom water temperature is around 2 °C. In addition, deep fresh water lakes may host gas hydrates as well, e.g. the fresh water Lake Baikal, Siberia. Continental deposits have been located in Siberia and Alaska in sandstone and siltstone beds at less than 800 m depth. Oceanic deposits seem to be widespread in the continental shelf (see Fig.) and can occur within the sediments at depth or close to the sediment-water interface. They may cap even larger deposits of gaseous methane.

Oceanic

There are two distinct types of oceanic deposit. The most common is dominated (> 99%) by methane contained in a structure I clathrate and generally found at depth in the sediment. Here, the methane is isotopically light (δ¹³C < −60‰), which indicates that it is derived from the microbial reduction of CO₂. The clathrates in these deep deposits are thought to have formed in situ from the microbially produced methane, since the δ¹³C values of clathrate and surrounding dissolved methane are similar. However, it is also thought that fresh water used in the pressurization of oil and gas wells in permafrost and along the continental shelves worldwide combines with natural methane to form clathrate at depth and pressure, since methane hydrates are more stable in fresh water than in salt water. Local variations may be very common, since the act of forming hydrate, which extracts pure water from saline formation waters, can often lead to local, and potentially significant, increases in formation water salinity. Hydrates normally exclude the salt in the pore fluid from which it forms, thus they exhibit high electric resistivity just like ice, and sediments containing hydrates have a higher resistivity compared to sediments without gas hydrates (Judge [67]).

These deposits are located within a mid-depth zone around 300–500 m thick in the sediments (the gas hydrate stability zone, or GHSZ) where they coexist with methane dissolved in the fresh, not salt, pore-waters. Above this zone methane is only present in its dissolved form at concentrations that decrease towards the sediment surface. Below it, methane is gaseous. At Blake Ridge on the Atlantic continental rise, the GHSZ started at 190 m depth and continued to 450 m, where it reached equilibrium with the gaseous phase. Measurements indicated that methane occupied 0-9% by volume in the GHSZ, and ~12% in the gaseous zone.

In the less common second type found near the sediment surface some samples have a higher proportion of longer-chain hydrocarbons (< 99% methane) contained in a structure II clathrate. Carbon from this type of clathrate is isotopically heavier (δ¹³C is −29 to −57 ‰) and is thought to have migrated upwards from deep sediments, where methane was formed by thermal decomposition of organic matter. Examples of this type of deposit have been found in the Gulf of Mexico and the Caspian Sea.

Some deposits have characteristics intermediate between the microbially and thermally sourced types and are considered to be formed from a mixture of the two.

The methane in gas hydrates is dominantly generated by microbial consortia degrading organic matter in low oxygen environments, with the methane itself produced by methanogenic archaea. Organic matter in the uppermost few centimeters of sediments is first attacked by aerobic bacteria, generating CO₂, which escapes from the sediments into the water column. Below this region of aerobic activity, anaerobic processes take over, including, successively with depth, the microbial reduction of nitrite/nitrate, metal oxides, and then sulfates are reduced to sulfides. Finally, once sulfate is used up, methanogenesis becomes a dominant pathway for organic carbon remineralization.

If the sedimentation rate is low (about 1 cm/yr), the organic carbon content is low (about 1% ), and oxygen is abundant, aerobic bacteria can use up all the organic matter in the sediments faster than oxygen is depleted, so lower-energy electron acceptors are not used. But where sedimentation rates and the organic carbon content are high, which is typically the case on continental shelves and beneath western boundary current upwelling zones, the pore water in the sediments becomes anoxic at depths of only a few centimeters or less. In such organic-rich marine sediments, sulfate then becomes the most important terminal electron acceptor due to its high concentration in seawater, although it too is depleted by a depth of centimeters to meters. Below this, methane is produced. This production of methane is a rather complicated process, requiring a highly reducing environment (Eh −350 to −450 mV) and a pH between 6 and 8, as well as a complex syntrophic consortia of different varieties of archaea and bacteria, although it is only archaea that actually emit methane.

In some regions (e.g., Gulf of Mexico) methane in clathrates may be at least partially derived from thermal degradation of organic matter, dominantly in petroleum. The methane in clathrates typically has a biogenic isotopic signature and highly variable δ¹³C (−40 to −100‰), with an approximate average of about −65‰ . Below the zone of solid clathrates, large volumes of methane may form bubbles of free gas in the sediments.

The presence of clathrates at a given site can often be determined by observation of a "bottom simulating reflector" (BSR), which is a seismic reflection at the sediment to clathrate stability zone interface caused by the unequal densities of normal sediments and those laced with clathrates. 

Gas hydrate pingos, have been discovered in the Arctic oceans Barents sea. Methane is bubbling from these dome like structures, with some of these gas flares extending close to the sea surface.

Reservoir size

The size of the oceanic methane clathrate reservoir is poorly known, and estimates of its size decreased by roughly an order of magnitude per decade since it was first recognized that clathrates could exist in the oceans during the 1960s and 1970s. The highest estimates (e.g. 3×10¹⁸ m³) were based on the assumption that fully dense clathrates could litter the entire floor of the deep ocean. Improvements in our understanding of clathrate chemistry and sedimentology have revealed that hydrates form in only a narrow range of depths (continental shelves), at only some locations in the range of depths where they could occur (10-30% of the Gas hydrate stability zone), and typically are found at low concentrations (0.9–1.5% by volume) at sites where they do occur. Recent estimates constrained by direct sampling suggest the global inventory occupies between 1×10¹⁵and 5×10¹⁵ m³ (0.24 to 1.2 million cubic miles). This estimate, corresponding to 500–2500 gigatonnes carbon (Gt C), is smaller than the 5000 Gt C estimated for all other geo-organic fuel reserves but substantially larger than the ~230 Gt C estimated for other natural gas sources. The permafrost reservoir has been estimated at about 400 Gt C in the Arctic, but no estimates have been made of possible Antarctic reservoirs. These are large amounts. In comparison, the total carbon in the atmosphere is around 800 gigatons. 

These modern estimates are notably smaller than the 10,000 to 11,000 Gt C (2×10¹⁶ m³) proposed by previous researchers as a reason to consider clathrates to be a geo-organic fuel resource (MacDonald 1990, Kvenvolden 1998). Lower abundances of clathrates do not rule out their economic potential, but a lower total volume and apparently low concentration at most sites does suggest that only a limited percentage of clathrates deposits may provide an economically viable resource.

Continental

Methane clathrates in continental rocks are trapped in beds of sandstone or siltstone at depths of less than 800 m. Sampling indicates they are formed from a mix of thermally and microbially derived gas from which the heavier hydrocarbons were later selectively removed. These occur in Alaska, Siberia, and Northern Canada. 

In 2008, Canadian and Japanese researchers extracted a constant stream of natural gas from a test project at the Mallik gas hydrate site in the Mackenzie River delta. This was the second such drilling at Mallik: the first took place in 2002 and used heat to release methane. In the 2008 experiment, researchers were able to extract gas by lowering the pressure, without heating, requiring significantly less energy. The Mallik gas hydrate field was first discovered by Imperial Oil in 1971-1972.

Commercial use

Economic deposits of hydrate are termed Natural Gas Hydrate (NGH) and are unique in that they store 164 m³ of methane, 0.8 m³ water in 1 m³ hydrate. Most NGH is found beneath the seafloor (95%) where it exists in thermodynamic equilibrium. The sedimentary methane hydrate reservoir probably contains 2–10 times the currently known reserves of conventional natural gas, as of 2013. This represents a potentially important future source of hydrocarbon fuel. However, in the majority of sites deposits are thought to be too dispersed for economic extraction. Other problems facing commercial exploitation are detection of viable reserves and development of the technology for extracting methane gas from the hydrate deposits.

In August 2006, China announced plans to spend 800 million yuan (US$100 million) over the next 10 years to study natural gas hydrates. A potentially economic reserve in the Gulf of Mexico may contain approximately 100 billion cubic metres (3.5×10¹² cu ft) of gas. Bjørn Kvamme and Arne Graue at the Institute for Physics and technology at the University of Bergen have developed a method for injecting CO₂ into hydrates and reversing the process; thereby extracting CH₄ by direct exchange. The University of Bergen's method is being field tested by ConocoPhillips and state-owned Japan Oil, Gas and Metals National Corporation (JOGMEC), and partially funded by the U.S. Department of Energy. The project has already reached injection phase and was analyzing resulting data by March 12, 2012.

On March 12, 2013, JOGMEC researchers announced that they had successfully extracted natural gas from frozen methane hydrate. In order to extract the gas, specialized equipment was used to drill into and depressurize the hydrate deposits, causing the methane to separate from the ice. The gas was then collected and piped to surface where it was ignited to prove its presence. According to an industry spokesperson, "It [was] the world's first offshore experiment producing gas from methane hydrate". Previously, gas had been extracted from onshore deposits, but never from offshore deposits which are much more common. The hydrate field from which the gas was extracted is located 50 kilometres (31 mi) from central Japan in the Nankai Trough, 300 meters (980 ft) under the sea. A spokesperson for JOGMEC remarked "Japan could finally have an energy source to call its own". The experiment will continue for two weeks before it is determined how efficient the gas extraction process has been. Marine geologist Mikio Satoh remarked "Now we know that extraction is possible. The next step is to see how far Japan can get costs down to make the technology economically viable." Japan estimates that there are at least 1.1 trillion cubic meters of methane trapped in the Nankai Trough, enough to meet the country's needs for more than ten years.

Both Japan and China announced in May 2017 a breakthrough for mining methane clathrates, when they extracted methane from hydrates in the South China Sea. However, industry consensus is that commercial-scale production remains years away.

Environmental concerns

Experts caution that environmental impacts are still being investigated and that methane—a greenhouse gas with around 25 times as much global warming potential over a 100-year period (GWP100) as carbon dioxide—could potentially escape into the atmosphere if something goes wrong. Furthermore, while cleaner than coal, burning natural gas also creates carbon emissions.

Hydrates in natural gas processing

Routine operations

Methane clathrates (hydrates) are also commonly formed during natural gas production operations, when liquid water is condensed in the presence of methane at high pressure. It is known that larger hydrocarbon molecules like ethane and propane can also form hydrates, although longer molecules (butanes, pentanes) cannot fit into the water cage structure and tend to destabilize the formation of hydrates. 

Once formed, hydrates can block pipeline and processing equipment. They are generally then removed by reducing the pressure, heating them, or dissolving them by chemical means (methanol is commonly used). Care must be taken to ensure that the removal of the hydrates is carefully controlled, because of the potential for the hydrate to undergo a phase transition from the solid hydrate to release water and gaseous methane at a high rate when the pressure is reduced. The rapid release of methane gas in a closed system can result in a rapid increase in pressure.

It is generally preferable to prevent hydrates from forming or blocking equipment. This is commonly achieved by removing water, or by the addition of ethylene glycol (MEG) or methanol, which act to depress the temperature at which hydrates will form (i.e. common antifreeze). In recent years, development of other forms of hydrate inhibitors have been developed, like Kinetic Hydrate Inhibitors (which by far slow the rate of hydrate formation) and anti-agglomerates, which do not prevent hydrates forming, but do prevent them sticking together to block equipment.

Effect of hydrate phase transition during deep water drilling

When drilling in oil- and gas-bearing formations submerged in deep water, the reservoir gas may flow into the well bore and form gas hydrates owing to the low temperatures and high pressures found during deep water drilling. The gas hydrates may then flow upward with drilling mud or other discharged fluids. When the hydrates rise, the pressure in the annulus decreases and the hydrates dissociate into gas and water. The rapid gas expansion ejects fluid from the well, reducing the pressure further, which leads to more hydrate dissociation and further fluid ejection. The resulting violent expulsion of fluid from the annulus is one potential cause or contributor to the "kick". (Kicks, which can cause blowouts, typically do not involve hydrates). 

Measures which reduce the risk of hydrate formation include:

• High flow-rates, which limit the time for hydrate formation in a volume of fluid, thereby reducing the kick potential.
• Careful measuring of line flow to detect incipient hydrate plugging.
• Additional care in measuring when gas production rates are low and the possibility of hydrate formation is higher than at relatively high gas flow rates.
• Monitoring of well casing after it is "shut in" (isolated) may indicate hydrate formation. Following "shut in", the pressure rises while gas diffuses through the reservoir to the bore hole; the rate of pressure rise exhibit a reduced rate of increase while hydrates are forming.
• Additions of energy (e.g., the energy released by setting cement used in well completion) can raise the temperature and convert hydrates to gas, producing a "kick".

Blowout recovery

Concept diagram of oil containment domes, forming upsidedown funnels in order to pipe oil to surface ships. The sunken oil rig is nearby.

 

At sufficient depths, methane complexes directly with water to form methane hydrates, as was observed during the Deepwater Horizon oil spill in 2010. BP engineers developed and deployed a subsea oil recovery system over oil spilling from a deepwater oil well 5,000 feet (1,500 m) below sea level to capture escaping oil. This involved placing a 125-tonne (276,000 lb) dome over the largest of the well leaks and piping it to a storage vessel on the surface. This option had the potential to collect some 85% of the leaking oil but was previously untested at such depths. BP deployed the system on May 7–8, but it failed due to buildup of methane clathrate inside the dome; with its low density of approximately 0.9 g/cm³ the methane hydrates accumulated in the dome, adding buoyancy and obstructing flow.

Methane clathrates and climate change

Methane is a powerful greenhouse gas. Despite its short atmospheric half life of 12 years, methane has a global warming potential of 86 over 20 years and 34 over 100 years (IPCC, 2013). The sudden release of large amounts of natural gas from methane clathrate deposits has been hypothesized as a cause of past and possibly future climate changes. Events possibly linked in this way are the Permian-Triassic extinction event and the Paleocene-Eocene Thermal Maximum. 

Climate scientists like James E. Hansen predict that methane clathrates in permafrost regions will be released because of global warming, unleashing powerful feedback forces that may cause runaway climate change.

Research carried out in 2008 in the Siberian Arctic found millions of tonnes of methane being released with concentrations in some regions reaching up to 100 times above normal.

In their Correspondence in the September 2013 Nature Geoscience journal, Vonk and Gustafsson cautioned that the most probable mechanism to strengthen global warming is large-scale thawing of Arctic permafrost which will release methane clathrate into the atmosphere. While performing research in July in plumes in the East Siberian Arctic Ocean, Gustafsson and Vonk were surprised by the high concentration of methane.

In 2014 based on their research on the northern United States Atlantic marine continental margins from Cape Hatteras to Georges Bank, a group of scientists from the US Geological Survey, the Department of Geosciences, Mississippi State University, Department of Geological Sciences, Brown University and Earth Resources Technology, claimed there was widespread leakage of methane.

Scientists from the Center for Arctic Gas Hydrate (CAGE), Environment and Climate at the Arctic University of Norway, published a study in June 2017, describing over a hundred ocean sediment craters, some 3,000 meters wide and up to 300 meters deep, formed due to explosive eruptions, attributed to destabilizing methane hydrates, following ice-sheet retreat during the last glacial period, around 12,000 years ago, a few centuries after the Bølling-Allerød warming. These areas around the Barents Sea, still seep methane today, and still existing bulges with methane reservoirs could eventually have the same fate.

Natural gas hydrates versus liquified natural gas in transportation

Since methane clathrates are stable at a higher temperature than liquefied natural gas (LNG) (−20 vs −162 °C), there is some interest in converting natural gas into clathrates rather than liquifying it when transporting it by seagoing vessels. A significant advantage would be that the production of natural gas hydrate (NGH) from natural gas at the terminal would require a smaller refrigeration plant and less energy than LNG would. Offsetting this, for 100 tonnes of methane transported, 750 tonnes of methane hydrate would have to be transported; since this would require a ship of 7.5 times greater displacement, or require more ships, it is unlikely to prove economically feasible.