Poly biaxial orientation

Soft-drink bottles made from poly(ethylene terephthalate) (PET) are usuady made by stretch-blow mol ding in a two-step process. Eirst, a test-tube-shaped preform is molded, which is then reheated to just above its glass-transition temperature, stretched, and blown. Stretching the PET produces biaxial orientation, which improves transparency, strength, and toughness of the botde (54,56). A one-step process is used for many custom containers that are injection stretch-blow molded. 

Biaxial orientation effects are of importance in the manufacture of films and sheet. Biaxially stretched poly(ethylene terephthalate) (e.g. Melinex),... 

Much of the success of the poly(ethylene terephthalate) bottle has arisen from the control of the biaxial orientation that occurs during manufacture to give a product both strong and of low gas permeability. 

Tubular film may be biaxially oriented by passing eooled film through a pair of nip rolls, reheating it to a uniform temperature and then passing it between a further pair of rolls. Between the two pairs of rolls a mandrel of air is introduced in order to expand the film. The proeess is similar to that shown for poly(vinylidene ehloride) in Figure 17.4. 

In the late 1970s several developments occurred causing renewed interest in poly(ethylene terephthalate) as a plastics material. These included the development of a new mouldable grade by ICI (Melinar) and the development of a blow moulding technique to produce biaxially oriented PET bottles. In addition there appeared a glass-fibre filled, ionomer nucleated, dibenzoate plasticised material by Du Pont (Rynite) (see Chapter 26). 

With the expiry of the basic ICI patents on poly(ethylene terephthalate) there was considerable development in terephthalate polymers in the early 1970s. More than a dozen companies introduced poly(butylene terephthalate) as an engineering plastics material whilst a polyether-ester thermoplastic rubber was introduced by Du Pont as Hytrel. Polyfethylene terephthalate) was also the basis of the glass-filled engineering polymer (Rynite) introduced by Du Pont in the late 1970s. Towards the end of the 1970s poly(ethylene terephthalate) was used for the manufacture of biaxially oriented bottles for beer, colas and other carbonated drinks, and this application has since become of major importance. Similar processes are now used for making wide-neck Jars. 

In this review the definition of orientation and orientation functions or orientation averages will be considered in detail. This will be followed by a comprehensive account of the information which can be obtained by three spectroscopic techniques, infra-red and Raman spectroscopy and broad line nuclear magnetic resonance. The use of polarized fluorescence will not be discussed here, but is the subject of a contemporary review article by the author and J. H. Nobbs 1. The present review will be completed by consideration of the information which has been obtained on the development of molecular orientation in polyethylene terephthalate and poly(tetramethylene terephthalate) where there are also clearly defined changes in the conformation of the molecule. In this paper, particular attention will be given to the characterization of biaxially oriented films. Previous reviews of this subject have been given by the author and his colleagues, but have been concerned with discussion of results for uniaxially oriented systems only2,3). 

Similarly, oriented crystallisation can be induced by stretching sheets or films of polymers in two directions simultaneously. The resulting materials have biaxially oriented polymer crystals. Typical examples of such materials are biaxially stretched poly(ethylene terephthalate), poly(vinylidene chloride), and poly (propylene). Since the oriented crystals do not interfere with light waves, such films combine good strength with high clarity, which makes them attractive in a number of applications. 

Stretching a polymer in two perpendicular directions, either successively or by blowing a bubble of molten material, leads to its biaxial orientation, which strongly improves mechanical properties in the stretching directions and/or gas permeability (e.g., biaxial orientation of polypropylene leads to BOPP (for biaxially oriented polypropylene) or biaxial orientation of poly(ethylene terephthalate) gives CC>2-impermeable bottles for carbonated beverages.) (Characterisation methods for determining molecular orientation are considered in Chapter 8.)... 

This stretching, similar to the drawing of fibres, which promotes orientation and crystallite formation, is called biaxial orientation. It gives the film added strength and gas-barrier properties. In some processes, monoaxial (uniaxial) drawing is employed, e.g., polypropylene, which is then slit into thin strips and fabricated into heavy duty sacks, carpet backing, etc. The stenter process is used to make biaxial oriented poly(vinylidene dichloride) ("ding" film), polyester, polyamide and polypropylene films. 

Biaxially Oriented Poly(Ethylene 2,6-Naphthalene) Films Manufacture, Properties and Commercial Applications... 

ISO 15988 2003 Plastics - Film and sheeting - Biaxially oriented poly(ethylene tereph-thalate) (PET) films... 

Poly(ethylene terephthalate) (PET), eg. DuPont Teijin Films Melinex polyester film, and poly(ethylene naphthalate) (PEN), eg. DuPont Teijin Films Teonex polyester film, are biaxially oriented semicrystalline films [1], The chemical structures of PET and PEN are shown in Fig. 7.1. 

Impact strength can be improved by other methods of modification—for example, by biaxial orientation of the material during or immediately after moulding. When transparent or translucent bottles are required in unplasticized poly(vinyl chloride) strength can be improved by including up to about 10% methyl-butadiene-styrene copolymers the bottles resulting retain a good finish. 

Ordered polymer films made from poly benzthiazole (PBZT) and poly benzoxazole (PBO) can be used as substrates for multilayer printed circuit boards and advanced interconnects to fill the current need for high speed, high density packaging. Foster-Miller, Inc. has made thin substrates (0.002 in.) using biaxially oriented liquid crystal polymer films processed from nematic solutions. PBZT films were processed and laminated to make a substrate with dielectric constant of 2.8 at 1 MHz, and a controllable CTE of 3 to 7 ppm/°C. The films were evaluated for use in multilayer boards (MLBs) which require thin interconnect substrates with uniform controllable coefficient of thermal expansion (CTE), excellent dielectric properties, low moisture absorption, high temperature capability, and simple reliable processing methods. We found that ordered polymer films surpass the limitations of fiber reinforced resins and meet the requirements of future chip-to-chip interconnection. 

When using poly (ethyleneterephthalate) PET, the preform is injection molded and rapidly cooled in the mold so that it remains amorphous (PET crystallizes very slowly). By heating it above its (65 °C), it passes into the rubbery state and can then be blown up and, simultaneously, longitudinally stretched. The biaxial orientation thus obtained accelerates the crystallization and, at the same time, results in a very fine crystalline texture so that a thin-walled, strong, transparent, and heat-resistant bottle is obtained. 

Biaxial orientation effects are important in the manufacture of films and sheet. Biaxially stretched polypropylene, poly(ethyleneterephthalate) (e.g., Melinex) and poly(vinylidene chloride) (Saran) produced by flat-film extrusion and tentering are strong films of high clarity. In biaxial orientation, molecules are randomly oriented in two dimensions just as fibers would be in a random mat the orientation-induced crystallization produces structures which do not interfere with the light waves. With polyethylene, biaxial orientation often can be achieved in blown-film extrusion. 

Figure 11-18. Stress/strain plot of a poly(ethyleneterephthalate) after different pretreatments u, undrawn st, biaxially oriented r, drawn and annealed. (After R. A. Hudson.)...

Guastavino J, Mary D, Krause E, Laurent C, Mayoux C. On the electrical properties of poly(ethylene naphthalate 2,6-dicar-boxylate) biaxially-oriented films. Polym Int 1998 46(l) 72-6. 

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