Shelf life Performance of PET

(Carbonated Beverages)
Y.Somasundaram

PET has become the choice of the carbonated beverages industry due to its excellent CO2 barrier properties compared to other polymers in the range. The barrier properties of polymer are achieved by the process known as the stretch blow molding. During the stretch blow molding process the polymer is oriented along the axial & hoop direction. During the bi-axial orientation process the polymer matrix has to be strain hardened above the Natural Stretch Ratio of the polymer (10 ~ 12 in case of a Co-PET, at lower blowing temperature (95 degC)).

The graph shows the stress strain curve of PET, for a proper stretch blow molding the bottle wall should be oriented above the start of strain hardening in steep slope region.

This is why different bottles have different sizes of preforms, even though they use the same weight of preform, which will ideally give the same wall thickness. Take for examples the two major, Coca Cola & Pepsi Cola, both of them have the 500ml pack size, Coke has 28gms preform with 100mm length, where as Pepsi has 27.7gms preform with 107 mm length. These changes in length and diameter of the preforms are required to ensure the required stretch ratio in range of 12, as Coke has a shorter bottle compared to that of Pepsi.

The following Table provides the difference in performance of Un-oriented PET (Preform) Vs Bi-axially oriented PET (Well blown PET bottle)
Property Thickness, mm (mil) Water Vapor Transmission Rate, g/m224h (g/100 in.224h) Oxygen Permeability, cm3mm/m224hatm (cm3mil/100 in.224hatm) Carbon Dioxide Permeability, cm3mm/m224hatm (cm3mil/100 in.224hatm) Tensile Modulus of Elasticity, MPa (psi) Tensile Stress @ Yield, MPa (psi) ASTM Method F372 D3985 D1434 D882 D882 Unoriented 0.25 (10) 6 (0.4) 5.1 (13) 28 (70) 2,200 (320,000) 57 (8,300) Oriented 0.36 (14) 2.3 (0.15) 2.2 (5.5) 14 (35) 4,960 (720,000) 172 (25,000)

From the table we understand that the CO2 barrier of the PET is increased two times, in bi-axial orientation (above the strain hardening limit). That is why PET is always stretch blow molded, though the other reason for the same is lower melt strength of the polymer at lower IV (0.74 dl/g to 0.90 dl/g). Thus in a PET bottle, getting the entire bottle wall to get oriented at the optimum level is always the great skill of the blow molding technician. The two major critical portion of a PET bottle, which gets poorly oriented are the Portion below the Neck Support Ring (NSR), Gate area. Here the polymer is stretched much below the Natural Stretch Ratio (NSR). These poorly oriented areas results in major loss of the CO2 in a carbonated beverage bottle, even though the proportion of the area under these two sections are less than 20%. The Natural stretch ratio of the PET, is not a fixed point like Melting point of the polymer, it varies depending on following factors; IV of the Preform. Temperature of preform during blowing. Moisture content of the preform. IV drop during the preform manufacturing. Rate of strain induced during the blowing process. Etc.

The following graphs indicate the movement of Natural Stretch Ratio, with variation in the process parameter.

The increase in IV results in reduction in the Natural Stretch Ratio

The increase in blowing temperature, results in increase in Natural Stretch Ratio.

The increase in moisture level in preform, can result in increase in Natural Stretch Ratio.

Thus two customers using the same resin, package design and equipments, can end up with a bottle of shelf life varying from 6 weeks to 10 weeks, depending on the processing systems adopted by him Look at a typical example; A processor with Lower IV drop in preform. Resultant Higher IV of preform. Lower temperature in blowing.(operating in the lower limit) Shorter preform storage period, before blowing. Better control on the bottle wall thickness. Lower base weight, & better wall base distribution. Better transition of wall thickness, below the NSR (Neck Support ring) Natural clear bottle, without colorant.

Will typically have 50% better shelf life performance than the processor, who has got all these wrong, even though, he will have the same resin, package design & equipments. Apart from the polymer properties the other weak point of the package, is the seal between the bottle lip surface and the wad of the cap. Major gas loss at this junction is due to the following facts; Unevenness in the lip surface during the preform molding. Any roughness created in the lip surface, created during handling of preform at higher temperatures, in the blow molder. In adequate torque during the capping operation. Poor quality of the wad, which wrinkle during the capping operation. Creep in the cap due to higher ambient conditions of storage.

Conclusion:
Thus, when a customer tells, he is having shelf life problem, with his package, it requires a big checklist and detailed understanding of his process, and systems to make improvement. What we have discussed till now is only the process & system aspect of lower shelf in carbonated beverages packaging. Of course, the storage and transportation, of the packed beverages, will again lead to drastic underperformance of the PET bottles, which will be discussed under Environmental aspects in PET packaging.