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Product failure of polymer
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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 USA 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 moulded. Attack of the acetal joint occurred because of faulty moulding leading to cracking along the threads of the fitting, which are serious stress concentrations.
Polymer oxidation leads to cracking and failure of the parts affected and 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.
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.
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Polymer oxidation leads to cracking and failure of the parts affected and 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.
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.
15.00 |
Chemical properties of polymers
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The attractive forces between polymer chains play a large part in determining a 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 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 polyethene can have a lower melting temperature compared to other polymers.
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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 polyethene can have a lower melting temperature compared to other polymers.
15.00 |
Petroleum
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Liquid geologically-extracted hydrocarbons are referred to as petroleum (literally "rock oil") or mineral oil, while gaseous geologic hydrocarbons are referred to as natural gas. All are significant sources of fuel and raw materials as a feedstock for the production of organic chemicals and are commonly found in the Earth's subsurface using the tools of petroleum geology.
The extraction of liquid hydrocarbon fuel from a number of sedimentary basins has been integral to modern energy development. Hydrocarbons are mined from tar sands, oil shale and potentially extracted from sedimentary methane hydrates. These reserves require distillation and upgrading to produce synthetic crude and petroleum.
Oil reserves in sedimentary rocks are the principal source of hydrocarbons for the energy, transport and petrochemical industries.
Hydrocarbons are of prime economic importance because they encompass the constituents of the major fossil fuels (coal, petroleum, natural gas, etc.) and its derivatives plastics, paraffin, waxes, solvents and oils. In urban pollution, these components--along with NOx and sunlight--all contribute to the formation of tropospheric ozone and greenhouse gases.
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The extraction of liquid hydrocarbon fuel from a number of sedimentary basins has been integral to modern energy development. Hydrocarbons are mined from tar sands, oil shale and potentially extracted from sedimentary methane hydrates. These reserves require distillation and upgrading to produce synthetic crude and petroleum.
Oil reserves in sedimentary rocks are the principal source of hydrocarbons for the energy, transport and petrochemical industries.
Hydrocarbons are of prime economic importance because they encompass the constituents of the major fossil fuels (coal, petroleum, natural gas, etc.) and its derivatives plastics, paraffin, waxes, solvents and oils. In urban pollution, these components--along with NOx and sunlight--all contribute to the formation of tropospheric ozone and greenhouse gases.
15.00 |
Polymer characterization
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The characterization of a polymer requires several parameters which need to be specified. This is because a polymer actually consists of a statistical distribution of chains of varying lengths, and each chain consists of monomer residues which affect its properties.
A variety of lab techniques are used to determine the properties of polymers. Techniques such as wide angle X-ray scattering, small angle X-ray scattering, and small angle neutron scattering are used to determine the crystalline structure of polymers. Gel permeation chromatography is used to determine the number average molecular weight, weight average molecular weight, and polydispersity. FTIR, Raman and NMR can be used to determine composition. Thermal properties such as the glass transition temperature and melting point can be determined by differential scanning calorimetry and dynamic mechanical analysis. Pyrolysis followed by analysis of the fragments is one more technique for determining the possible structure of the polymer. Thermogravimetry is a useful technique to evaluate the thermal stability of the polymer. Detailed analyses of TG curves also allow us to know a bit of the phase segregation in polymers.
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A variety of lab techniques are used to determine the properties of polymers. Techniques such as wide angle X-ray scattering, small angle X-ray scattering, and small angle neutron scattering are used to determine the crystalline structure of polymers. Gel permeation chromatography is used to determine the number average molecular weight, weight average molecular weight, and polydispersity. FTIR, Raman and NMR can be used to determine composition. Thermal properties such as the glass transition temperature and melting point can be determined by differential scanning calorimetry and dynamic mechanical analysis. Pyrolysis followed by analysis of the fragments is one more technique for determining the possible structure of the polymer. Thermogravimetry is a useful technique to evaluate the thermal stability of the polymer. Detailed analyses of TG curves also allow us to know a bit of the phase segregation in polymers.
05.00 |
Polymer degradation
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Polymer degradation is a change in the properties—tensile strength, colour, shape, etc.—of a polymer or polymer-based product under the influence of one or more environmental factors, such as heat, light or chemicals. It is often due to the hydrolysis of the bonds connecting the polymer chain, which in turn leads to a decrease in the molecular mass of the polymer. These changes may be undesirable, such as changes during use, or desirable, as in biodegradation or deliberately lowering the molecular mass of a polymer. Such changes occur primarily because of the effect of these factors on the chemical composition of the polymer. Ozone cracking and UV degradation are specific failure modes for certain polymers.
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 linkages (bonds) that hold the atoms of the polymer together. When heated above 450°C it degrades to form a mixture of hydrocarbons. Other polymers—like polyalphamethylstyrene—undergo specific chain scission with breakage occurring only at the ends. They literally unzip or depolymerize to become the constituent monomer.
However, the degradation process can be useful from the viewpoints of understanding the structure of a polymer or recycling/reusing the polymer waste to prevent or reduce environmental pollution. Polylactic acid and polyglycolic acid, for example, are two polymers that are useful for their ability to degrade under aqueous conditions. A copolymer of these polymers is used for biomedical applications, such as hydrolysable stitches that degrade over time after they are applied to a wound. These materials can also be used for plastics that will degrade over time after they are used and will therefore not remain as litter.
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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 linkages (bonds) that hold the atoms of the polymer together. When heated above 450°C it degrades to form a mixture of hydrocarbons. Other polymers—like polyalphamethylstyrene—undergo specific chain scission with breakage occurring only at the ends. They literally unzip or depolymerize to become the constituent monomer.
However, the degradation process can be useful from the viewpoints of understanding the structure of a polymer or recycling/reusing the polymer waste to prevent or reduce environmental pollution. Polylactic acid and polyglycolic acid, for example, are two polymers that are useful for their ability to degrade under aqueous conditions. A copolymer of these polymers is used for biomedical applications, such as hydrolysable stitches that degrade over time after they are applied to a wound. These materials can also be used for plastics that will degrade over time after they are used and will therefore not remain as litter.
15.00 |
Furan
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Furan; One of a class of heterocyclic aromatic compounds characterized by five-membered ring structure consisting of four CH2 groups and one oxygen atom. The simplest furan compound is furan itself; a clear, volatile and mildly toxic liquid; melts at -86 0C, boils at 32 0C, insoluble in water, soluble in alcohol and ether. In the absence of inhibitors, it may form peroxides and and accumulate peroxides which may explode when subjected to heat or shock. It may discolor on exposure to air. This material is hazardous when peroxide levels are concentrated by distillation or evaporation. It can be stabilized with BHT. It can be obtained from wood oils. It is used as a solvent as well as in the synthesis of furfural and other organic compounds. It is converted to more important solvent, tetrahydrofuran by hydrogenation. Niitro-substituted furan derivatives are used as biocides or fungicides to inhibit bacterial growth. Sulfur-substituted furan derivatives are used as flavouring agents. Furfural (Furfuraldehyde), a derivative of furan, is a viscous, colorless liquid that has a pleasant aromatic odor; upon exposure to air it turns dark brown or black; boils at about 160 0C; soluble in ethanol, ether and somewhat in water. It is commonly used as a solvent. Furfural is the aldehyde of pyromucic acid; it has properties similar to those of benzaldehyde. It is prepared commercially by dehydration of pentose sugars obtained from cornstalks and corncobs, husks of oat and peanut, and other waste products. The major application of furfural is being use as a feedstock for furfuryl alcohol. The most commercial quantity of furfuryl alcohol is used in the production of thermosetting furan resin and furan cement, strong adhesive, in which the furan ring is an integral part of the polymer chain providing highly resistance to chemicals. Furfural is used as a solvent for refining lubricating oils and butadiene extraction. It is used as a fungicide and weed killer. It is used in the production of tetrahydrofuran (THF), saturated form of furan. THF is one of the most polar ethers. It is used as an important industrial solvent recognized for its unique combination of useful properties. It is a colorless, volatile cycloaliphatic (5-membered) ether with a characteristic odor; boiling point at 66 0C; soluble in water and organic solvents. THF is unstable at room temperature due to possibility of peroxide formation; stabilized sometimes with BHT. Its unhindered oxygen atom carries two unshared pairs of electrons - a structure which favors the formation of coordination complexes and the solvation of cations. THF is made also by eliminating water from 1,4-butanediol. THF is used as an useful chemical intermediate especially as a starting materials for the preparation of nylon.
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15.00 |
Density
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The density of a material is defined as its mass per unit volume:
Different materials usually have different densities, so density is an important concept regarding buoyancy, metal purity and packaging.
In some cases density is expressed as the dimensionless quantities specific gravity or relative density, in which case it is expressed in multiples of the density of some other standard material, usually water or air.
Density is a characteristic of a substance; mass and volume are not. Mass and volume vary with size but density will remain constant.Temperature will affect the density of a substance and the temperature at which density for that substance was determined is usually reported along with the density value.
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Different materials usually have different densities, so density is an important concept regarding buoyancy, metal purity and packaging.
In some cases density is expressed as the dimensionless quantities specific gravity or relative density, in which case it is expressed in multiples of the density of some other standard material, usually water or air.
Density is a characteristic of a substance; mass and volume are not. Mass and volume vary with size but density will remain constant.Temperature will affect the density of a substance and the temperature at which density for that substance was determined is usually reported along with the density value.
15.00 |
Polymer (part 3)
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Tensile strength
The tensile strength of a material quantifies how much stress the material will endure before failing. 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.
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.
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.
Melting point
The term melting point, when applied to polymers, suggests not a solid-liquid phase transition but a transition from a crystalline or semi-crystalline phase to a solid amorphous phase. Though abbreviated as simply Tm, the property in question is more properly called the crystalline melting temperature. Among synthetic polymers, crystalline melting is only discussed with regards to thermoplastics, as thermosetting polymers will decompose at high temperatures rather than melt.
Boiling point
The boiling point of a polymer substance is never defined because polymers will decompose before reaching theoretical boiling temperatures.
06.00 |
Polymer (part 2)
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The structural properties of a polymer relate to the physical arrangement of monomer residues along the backbone of the chain. Structure has a strong influence on the other properties of a polymer. For example, a linear chain polymer may be soluble or insoluble in water depending on whether it is composed of polar monomers (such as ethylene oxide) or nonpolar monomers (such as styrene). On the other hand, two samples of natural rubber may exhibit different durability, even though their molecules comprise the same monomers. Polymer scientists have developed terminology to describe precisely both the nature of the monomers as well as their relative arrangement.
Monomer identity
The identity of the monomers comprising the polymer is generally the first and most important attribute of a polymer. The repeat unit is the constantly repeated unit of the chain and is also characteristic of the polymer. Polymer nomenclature is generally based upon the type of monomers comprising the polymer. Polymers that contain only a single type of monomer are known as homopolymers, while polymers containing a mixture of monomers are known as copolymers. Poly(styrene), for example, is composed only of styrene monomers, and is therefore classified as a homopolymer. Ethylene-vinyl acetate, on the other hand, contains more than one variety of monomer and is thus a copolymer. Some biological polymers are composed of a variety of different but structurally related monomers, such as polynucleotides composed of nucleotide subunits.
The repeating unit of the polymer may be different from the starting monomer(s), for example in condensation polymerization. A simple example is 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.
A polymer molecule containing ionizable subunits is known as a polyelectrolyte. An ionomer is a subclass of polyelectrolyte with a low fraction of ionizable subunit.
Polymer properties
Types of polymer properties can be broadly divided into several categories based upon scale. At the nano-micro scale there are properties that directly describe the chain itself, and can be thought of as polymer structure. At an intermediate mesoscopic level there are properties that describe the morphology of the polymer matrix in space. At the macroscopic level properties describe the bulk behavior of the polymer.
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.
Relationship between chain length and polymer properties
Polymer bulk properties are strongly dependent upon their structure and mesoscopic behavior. A number of qualitative relationships between structure and properties are known.
Increasing chain length tends to decrease chain mobility, increase strength and toughness, and increase the glass transition temperature (Tg). 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. Chain length is related to melt viscosity roughly as 1:103.2, so that a tenfold increase in polymer chain length results in a viscosity increase of over 1000 times.
06.00 |
Polymer (part 1)
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A polymer is a large molecule (macromolecule) composed of repeating structural units typically connected by covalent chemical bonds. While polymer in popular usage suggests plastic, the term actually refers to a large class of natural and synthetic materials with a variety of properties and purposes.
Well-known examples of polymers include plastics and proteins. A simple example is polypropylene, whose repeating unit structure is shown at the right. However, polymers are not just limited to having predominantly carbon backbones, elements such as silicon form familiar materials such as silicones, examples being silly putty and waterproof plumbing sealant. The backbone of DNA is in fact based on a phosphodiester bond.
Natural polymer materials such as shellac and amber have been in use for centuries. Biopolymers such as proteins and nucleic acids play crucial roles in biological processes. A variety of other natural polymers exist, such as cellulose, which is the main constituent of wood and paper.
The list of synthetic polymers includes Bakelite, neoprene, nylon, PVC, polystyrene, polyacrylonitrile, PVB, silicone, and many more.
Polymers are studied in the fields of polymer chemistry, polymer physics, and polymer science.
• Functionality
This characteristic of a monomer helps in deciding whether a particular monomer can form a polymer or not. It is actually defined as the number of reaction sites present around the monomer in order to help in forming chemical covalent bonds,so that it can form a polymer.
The basic required functionality is 2.
• Polymer synthesis
Polymerization is the process of combining many small molecules known as monomers into a covalently bonded chain. During the polymerization process, some chemical groups may be lost from each monomer. The distinct piece of each monomer that is incorporated into the polymer is known as a repeat unit or monomer residue.
• Laboratory synthesis
Laboratory synthetic methods are generally divided into two categories, condensation polymerization and addition polymerization. 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. Efforts towards rational synthesis of biopolymers via laboratory synthetic methods, especially artificial synthesis of proteins, is an area of intense research.
• Biological synthesis
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 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.
Modification of natural polymers
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 sulphur.
Modification of natural polymers
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 sulphur.
06.00 |
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