Polymers barrier properties

In food contact materials, polymer nanocomposites-based packaging materials are developed by the inclusion of nanoscale fillers resulting in clear improvement of food quality and extension of the shelf-life through minimizing microbial growth. They can serve not only as barriers to moisture, water vapour, gases and solutes, but also as carriers of some active substances. The enhancement of the polymer barrier properties is the most obvious application of nanocomposites in the food industry. 

It possesses outstanding barrier properties to gases, especially water vapor. It is surpassed only by the fully fiuorinated polymers in chemical resistance. A few solvents dissolve it at temperatures... 

In the late 1960s a new class of AN copolymers and multipolymers was introduced that contain >60% acrylonitrile. These are commonly known as barrier resins and have found thek greatest acceptance where excellent barrier properties toward gases (5), chemicals, and solvents are needed. They may be processed into bottles, sheets, films, and various laminates, and have found wide usage in the packaging industry (see Barrier polymers). 

Poly(vinyhdene chloride) (PVDC) film has exceUent barrier properties, among the best of the common films (see Barrier polymers). It is formulated and processed into a flexible film with cling and tacky properties that make it a useful wrap for leftovers and other household uses. As a component in coatings or laminates it provides barrier properties to other film stmctures. The vinyUdene chloride is copolymerized with vinyl chloride, alkyl acrylates, and acrylonitrile to get the optimum processibUity and end use properties (see Vinylidene chloride monomer and polymers). 

Figure 4c also describes the spontaneous polymerisation ofpara- s.yX en.e diradicals on the surface of soHd particles dispersed in a gas phase that contains this reactive monomer (16) (see XylylenePOLYMERS). The poly -xylylene) polymer produced forms a continuous capsule sheU that is highly impermeable to transport of many penetrants including water. This is an expensive encapsulation process, but it has produced capsules with impressive barrier properties. This process is a Type B encapsulation process, but is included here for the sake of completeness. 

An excellent review of composite RO and nanofiltration (NE) membranes is available (8). These thin-fHm, composite membranes consist of a thin polymer barrier layer formed on one or more porous support layers, which is almost always a different polymer from the surface layer. The surface layer determines the flux and separation characteristics of the membrane. The porous backing serves only as a support for the barrier layer and so has almost no effect on membrane transport properties. The barrier layer is extremely thin, thus allowing high water fluxes. The most important thin-fHm composite membranes are made by interfacial polymerization, a process in which a highly porous membrane, usually polysulfone, is coated with an aqueous solution of a polymer or monomer and then reacts with a cross-linking agent in a water-kniniscible solvent. 

Barrier Properties. VinyUdene chloride polymers are more impermeable to a wider variety of gases and Hquids than other polymers. This is a consequence of the combination of high density and high crystallinity in the polymer. An increase in either tends to reduce permeabiUty. A more subtle factor may be the symmetry of the polymer stmcture. It has been shown that both polyisobutylene and PVDC have unusually low permeabiUties to water compared to their monosubstituted counterparts, polypropylene and PVC (88). The values Hsted in Table 8 include estimates for the completely amorphous polymers. The estimated value for highly crystalline PVDC was obtained by extrapolating data for copolymers. 

The excellent chemical resistance and physical properties of PVA resins have resulted in broad industrial use. The polymer is an excellent adhesive and possesses solvent-, oil-, and grease-resistant properties matched by few other polymers. Poly(vinyl alcohol) films exhibit high tensile strength, abrasion resistance, and oxygen barrier properties which, under dry conditions, are superior to those of any other known polymer. The polymer s low surface tension provides for excellent emulsification and protective coUoid properties. 

Several physical factors can affect the barrier properties of a polymer. These include temperature, humidity, orientation, and cross-linking. 

Layered Structures. Whenever a barrier polymer lacks the necessary mechanical properties for an appHcation or the barrier would be adequate with only a small amount of the more expensive barrier polymer, a multilayer stmcture via coextmsion or lamination is appropriate. Whenever the barrier polymer is difficult to melt process or a particular traditional substrate such as paper or cellophane [9005-81-6] is necessary, a coating either from latex or a solvent is appropriate. A layered stmcture uses the barrier polymer most efficiently since permeation must occur through the barrier polymer and not around the barrier polymer. No short cuts are allowed for a permeant. The barrier properties of these stmctures are described by the permeance which is described in equation 16 where and L are the permeabiUties and thicknesses of the layers. 

Immiscible Blends. When two polymers are blended, the most common result is a two-phase composite. The most interesting blends have good adhesion between the phases, either naturally or with the help of an additive. The barrier properties of an immiscible blend depend on the permeabihties of the polymers, the volume fraction of each, phase continuity, and the aspect ratio of the discontinuous phase. Phase continuity refers to which phase is continuous in the composite. Continuous for barrier appHcations means that a phase connects the two surfaces of the composite. Typically, only one of the two polymer phases is continuous, with the other polymer phase existing as islands. It is possible to have both polymers be continuous. 

Measuring the barrier properties of polymers is important for several reasons. The effects of formulation or process changes need to be known, new polymers need to be evaluated, data are needed for a new apphcation before a large investment has been made, and fabricated products need to have performance verified. For some apphcations a full range of data is necessary, including P, Z9, and S plus the effects of temperature and humidity. 

In 1977, consumption of PET resin in bottie appHcations was dramatically increased when the EDA banned competing acrylonitrile resins owing to toxicity considerations (recentiy rescinded) (69) and when the 2 L bottie was accepted for beverage sales worldwide (70). The carbon dioxide barrier properties of PET are sufficient to provide the six-month shelf life necessary for carbonated beverages (qv) (see also Barrier polymers). 

In order to reduce the tendency of the film to shrink oriented film may be annealed at about 100°C whilst under tension immediately after drawing. The film is often coated with another polymer sueh as a vinylidene ehloride-based copolymer. This both improves the barrier properties and improves the heat scalability. 

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