Influence of flavour absorption on oxygen permeation ...

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Influence of flavour absorption on oxygen permeation through LDPE, PP, PC and PET plastics food packaging a

a

b

R. W. G. van Willige , J. P. H. Linssen , M. B. J. Meinders , H. J. van der c

Stege & A. G. J. Voragen

d

a

Laboratory of Food Chemistry, Department of Agrotechnology and Food Sciences, Wageningen University, PO Box 8129, 6700 EV Wageningen, The Netherlands b

ATO Agrotechnological Research Institute/Wageningen Centre for Food Sciences, Department of Food Structure and Functionality, Bornsesteeg 59, Wageningen, The Netherlands c

Laboratory of Product Design and Quality Management, Department of Agrotechnology and Food Sciences, Wageningen University, PO Box 8129, 6700 EV Wageningen, The Netherlands d

Laboratory of Food Chemistry, Department of Agrotechnology and Food Sciences, Wageningen University, PO Box 8129, 6700 EV Wageningen, The Netherlands; [email protected] Published online: 10 Nov 2010.

To cite this article: R. W. G. van Willige , J. P. H. Linssen , M. B. J. Meinders , H. J. van der Stege & A. G. J. Voragen (2002) Influence of flavour absorption on oxygen permeation through LDPE, PP, PC and PET plastics food packaging, Food Additives & Contaminants, 19:3, 303-313, DOI: 10.1080/02652030110081146 To link to this article: http://dx.doi.org/10.1080/02652030110081146

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Food Additives and Contaminants , 2002, Vol. 19, No. 3, 303 ± 313

In¯uence of ¯avour absorption on oxygen permeation through LDPE, PP, PC and PET plastics food packaging


R. W. G. van Willigey, J. P. H. Linsseny, M. B. J. Meinders}, H. J. van der Stege‡ and A. G. J. Vorageny* y Laboratory of Food Chemistry and ‡ Product Design and Quality Management, Department of Agrotechnology and Food Sciences, Wageningen University, PO Box 8129, 6700 EV Wageningen, The Netherlands } ATO Agrotechnological Research Institute/Wageningen Centre for Food Sciences, Department of Food Structure and Functionality, Bornsesteeg 59, Wageningen, The Netherlands

(Received 16 January 2001; revised 2 July 2001; accepted 17 July 2001)

The eŒect of ¯avour absorption on the oxygen permeability of low-density polyethylene (LDPE), polypropylene (PP), polycarbonat e (PC) and polyethylene terephthalate (PET) was studied using an isostatic continuous ¯ow system. Polymer samples were exposed to a model solution containing limonene, hexyl acetate, nonanone and decanal at 40°C. After exposure, one part of each sample was analysed for absorbed ¯avour compounds using a Large Volume Injection GC Ultrasonic ìn vial’ extraction method, and from the other part, oxygen permeability was measured in a permeation cell at 25°C. After 8 h of exposure, LDPE and PP samples showed a signi®cant linear (R2 ˆ 0:82 and 0.99) increase in oxygen permeability of 21 and 130%, respectively. Owing to swelling of the polymer samples resulting from ¯avour absorption, the structure of the polymeric network changed (i.e. opened) and consequently increased oxygen permeability. The oxygen permeabilit y of exposed PC showed a signi®cant linear (R2 ˆ 0:78) decrease of 11% after 21 days. PC obviously did not swell like LDPE or PP. Therefore, it was suggested that absorbed ¯avour compounds occupied or blocked `microcavities’ through which normally oxygen is transported. Absorption of ¯avour compounds by PET did not aŒect the oxygen permeability of PET signi®cantly.

* To whom correspondence should be addressed. e-mail: Fons. [email protected]

Keywords : absorption, ¯avour compound, packaging, oxygen permeability, LDPE, PP, PC, PET

Introduction An important requirement in selecting food-packaging systems is the barrier properties of the packaging material. Barrier properties include permeability of gases (such as O2 , CO2 , N2 and ethylene), water vapour, aroma compounds and light. These are vital factors for maintaining the quality of foods. A good barrier to moisture and oxygen keeps a product crisp and fresh and reduces oxidation of food constituents. Plastics are widely used for food packaging due to their ¯exibility, variability in size and shape, thermal stability, and barrier properties. Polyethylene (PE) and polypropylene (PP) have been used for many years because of their good heat sealability, low costs and low water vapour permeability. However, poor gas permeability makes laminating of PE with aluminium foil and paper necessary. During the last few decades, polyethylene terephthalate (PET) and, to a lesser extent, polycarbonate (PC) have found increased use for food packaging. PET has good mechanical properties, excellent transparency and relatively low permeability to gases. PC is tough, stiŒ, hard and transparent, but has poor gas permeability properties and is still quite expensive. Unlike glass, plastics are not inert allowing mass transport of compounds such as water, gases, ¯avours, monomers and fatty acids between a food product, package and the environment due to permeation, migration and absorption. The quality and shelf-life of plastic-packaged food depend strongly on physical and chemical properties of the polymeric ®lm and the interactions between food components and package during storage. Several investigations showed that considerable amounts of aroma compounds can be absorbed by plastic packaging materials, resulting in loss of aroma

Food Additives and Contaminant s ISSN 0265±203X print/ISSN 1464±5122 online # 2002 Taylor & Francis Ltd http://www.tandf.co.uk/journals DOI: 10.1080/0265203011008114 6


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R. W. G. van Willige et al.

intensity or an unbalanced ¯avour pro®le (Arora et al. 1991, Linssen et al. 1991, Nielsen et al. 1992, Paik 1992, LebosseÂ et al. 1997, van Willige et al. 2000a, b). Absorption may also indirectly aŒect the food quality by causing delamination of multilayer packages (Olafsson and Hildingsson 1995, Olafsson et al. 1995) or by altering the barrier and mechanical properties of plastic packaging materials (Taw®k et al. 1998). Oxygen permeability through the packaging is an important factor for the shelf-life of many packed foods. Little information is available in literature about the in¯uence of absorbed compounds on the oxygen permeability of packaging materials. Hirose et al. (1988) reported that the oxygen permeability of LDPE and two types of ionomer increased due to the presence of absorbed d-limonene. Johansson and Leufven (1994) studied the eŒect of rapeseed oil on the oxygen barrier properties of diŒerent polymer packaging materials. They found that amorphous PET remained an excellent oxygen barrier even after storage in rapeseed oil for 40 days. The polyole®ns (PP and high-density PE) showed an increased oxygen transmission rate (OTR) after being in contact with rapeseed oil for 40 days. This was attributed to swelling of the polymer matrix. However, the increase in OTR was not proportional to the amount of absorbed oil. Sadler and Braddock (1990) showed that the oxygen permeability of LDPE was proportional to the mass of absorbed limonene. In another paper, they concluded that oxygen permeability of LDPE and the diŒusion coe cients of citrus ¯avour volatiles in LDPE were related to the solubility of these compounds in the polymer (Sadler and Braddock 1991). The increased oxygen permeability of LDPE could only be explained by absorption. Attachment of volatile molecules at the polymer surface (adsorption) might hinder oxygen permeation, which would lower the oxygen permeation, or leave it unchanged. An increased oxygen permeability of LDPE indicated that absorption of volatiles must be responsible for structural changes in the polymer. Flavour absorption can have a major in¯uence on the oxygen permeability of plastic packaging materials, and consequently on the shelflife of a food product, making it necessary to investigate this important aspect more thoroughly. In this paper, the in¯uence of ¯avour absorption on the oxygen permeability of LDPE, PP, PC and PET was investigated.

Materials and methods Materials The polymer packaging materials used were lowdensity polyethylene (LDPE; LDPE 300R; thickness 100 mm; Dow Benelux NV, Terneuzen, The Netherlands), oriented polypropylen e (PP; Bicor1 MB200; 30 mm; Mobil Plastics Europe, Kerkrade, The Netherlands), polycarbonate (PC; Lexan1 8B35; 75 mm; General Electric Plastics, Bergen op Zoom, The Netherlands) and polyethylene terephthalate (PET; Melinex1 800; 12 mm; DuPont Teijin Films, Luxembourg). Decanal and 2-nonanone were purchased from Merck, hexyl acetate from Aldrich and (+)-limonene from Sigma. Tween 80 from Merck was used as an emulsi®er to disperse the ¯avour compounds in an aqueous phase. Selection of the aroma compounds was based on diŒerences in functional groups, polarity and absorption a nity by the diŒerent polymers. Characteristics of the ¯avour compounds are listed in table 1. Log P represents the hydrophobicit y of a ¯avour compound; a higher log P means a more hydrophobic compound.

Preparation of ¯avour model solutions A ¯avour model solution was prepared in a stoppered conical ¯ask by dispersing the aroma compounds (100 ml l 1 each) in 4 g l 1 aqueous Tween 80. Each ¯avour compound was added using a micropipet (Micropipette) equipped with a glass capillary tube (Socorex, Lausanne, Switzerland). An Ultra Turrax Table 1. Characteristics of the ¯avour compounds used in the model solutions. Flavour compound

bp (°C) Log Pa

Limonene Decanal 2-Nonanone Hexyl acetate

178 208 192 168

a

4.58 4.09 3.30 2.83

Solubilityb (g l 1 )

Density (g ml 1 )

Purity (%)

0.0027 0.012 0.21 0.37

0.84 0.83 0.82 0.88

99 97 99 99

Measure of hydrophobicity, calculated with ACD/log P v. 3.6 (www.acdlabs.com). b Solubility at 25°C in water, calculated with ACD/aqueous solubility v. 4.0 (www.acdlabs.com).

Flavour absorption, oxygen permeation and plastics food packaging

T25 (IKA-Labortechnik, Staufen, Germany) was used for homogenization for 2 min at 9500 rpm, followed by equilibration overnight in the dark at 40°C.


Exposure conditions Each polymer specimen (11 11 cm) was bent and stapled together with two galvanized staples. Four of the stapled polymer specimens were fully immersed in 1 litre of an equilibrated model solution containing one or more ¯avour compounds and incubated in the dark at 40°C. Polymer samples immersed in Tween 80 model solution without ¯avour compounds were used as a blank. DiŒerent exposure times were used to achieve diŒerent absorbed ¯avour quantities in the polymers. After exposure, a polymer sample was removed from the model solution, rinsed with ethanol for 10 s and thoroughly wiped with paper tissue to remove excess of the model solution. Polymer samples were divided into two parts. One part was analysed for absorbed ¯avour compounds using a large volume injection gas chromatography (LVI-GC) ultrasonic ìn vial’ extraction method. The other part of the sample was placed in a permeation cell to measure the oxygen permeability.

LVI-GC ìn-vial’ extraction of the polymer strips Strips of LDPE (1.5 2.0 cm), PP (1.5 2.0 cm), PC (1.5 11.0 cm) and PET (3.0 11.0 cm) were cut in small pieces and immediately placed into a 10-ml vial containing 5 ml n-hexane (Enviroscan, Labscan, Dublin, Ireland). The vials were tightly closed with a Te¯on silicone seal and an aluminium crimp cap.

Figure 1. Schematic view of the oxygen permeability system.

305

In-vial extraction was carried out for 60 min in an ultrasonic bath (Ultrawave, CardiŒ, UK). Longer ultrasonic treatment did not achieve better extraction. GC analysis was performed using a LVI-GC system (Ultra TraceTM ) (Interscience, Breda, The Netherlands). The background of this technique and equipment used have been described by van Willige et al. (2000a). The following LVI-GC parameters were kept constant for all hexane extracts: helium as carrier gas at a constant ¯ow of 2.3 ml min 1 ; FID detector temperature at 290°C; solvent vapour exit (SVE) temperature at 200°C; oven temperature programme from 50°C (held 10 min) at a rate of 5°C min 1 to 150 °C and further at a rate of 25°C min 1 to 280°C (held 5 min). The conditions for the LDPE, PP or PC hexane extracts were: injection volume 30 ml, injection speed 5 ml s 1 , SVE delay time and secondary cooling time 11 s. The conditions for the PET hexane extracts were: injection volume 200 ml, injection speed 2 ml s 1 , SVE delay time and secondary cooling time 50 s. Calibration curves …r2 > 0:997 † were established for each component with the external standard method.

Determination of oxygen permeability To measure the oxygen permeability of the exposed polymer specimens a set-up based on the isostatic continuous ¯ow technique was developed (®gure 1). In the isostatic method, the pressure diŒerential across the test ®lm remains constant during the total permeation process. Whereas the high-pressure side (oxygen chamber) remains constant at a certain value, the low-pressure side (nitrogen chamber) is maintained by sweeping the permeated molecules by a

R. W. G. van Willige et al.

306

Ft 4 1=2 ˆ p X exp … X † º Fmax


continuous ¯ow of carrier gas (Hernandez and Gavara 1999). A stainless steel two-chamber permeation cell was maintained in a temperature-controlled cabinet at 25 0:1°C. O-rings were used to ensure airtightness. To remove oxygen, both chambers and polymer ®lm were ¯ushed with dry nitrogen 5.0 (Hoekloos, Schiedam, The Netherlands) for 20 min. The ¯ow rate was maintained at a constant ¯ow of 1.5 l h 1 using calibrated mass ¯ow controllers from Brooks Instruments (Veenendaal, The Netherlands). Initial time was marked when the oxygen 2.5 (Hoekloos) gas stream started to ¯ow through the oxygen chamber. The amount of oxygen permeated per unit time was monitored continuously for 30 min, which was su cient to reach a maximum permeation. Oxygen concentrations were measured with a Xentra 4100 Gas Purity Analyser (Servomex, Zoetermeer, The Netherlands) equipped with a Zirconia O2 measuring cell. The gas analyser was calibrated periodically using oxygen±nitrogen mixtures with accurately known oxygen content. Preliminary experiments showed that due to the high operation temperature of the Zirconia measuring cell ( 750 °C), burning of desorbed ¯avour compounds occurred, consequently decreasing the oxygen readings. Therefore, tubes ®lled with Tenax1 -TA absorbance (Alltech, Zoetermeer, The Netherlands) were placed between the permeation cell and the gas analyser to prevent entering desorbed ¯avour compounds into the Zirconia measuring cell. Equal pressure between the two chambers was maintained by placing also Tenax tubes at the exit of the oxygen chamber. The permeability coe cient P was determined directly from the maximum by: Pˆ

Fmax l A p

where Ft is the oxygen ¯ow at time t and X ˆ l 2 =4Dt. The mathematical method of Newton±Raphson was used to evaluate X as a function of time. The diŒusion coe cient is determined from the slope of 1/X versus t for values within the range 0:05 < Ft =Fmax < 0:95 (Hernandez et al. 1986). The solubility coe cient S describes the amount of the transferring molecules retained or dissolved in the ®lm at equilibrium conditions. When Henry’s law of solubility holds, the solubility coe cient S can be calculated from: PˆD S !S ˆ

P D

Desorption of ¯avour compounds from PP ®lm During all oxygen permeability measurements desorption of ¯avour compounds from the plastic ®lms occurred. The rate of ¯avour desorption from PP ®lm was investigated after 3 days of exposure to the ¯avour model solution at 40°C. Preliminary experiments showed that PP reached an absorption equilibrium after 3 days. After 10, 20, 30, 40, 50, 60, 90 and 120 min, the oxygen permeability experiment was stopped and the ®lm removed from the permeation cell. Two strips (1:5 2:0 cm) were cut from the centre of the ®lm to analyse the amount of ¯avour compounds left.

Results PP and LDPE

where Fmax is the maximum ¯ow of the oxygen (quantity per time), l is the ®lm thickness, A is the area of the ®lm exposed to oxygen and p is the driving force or gas pressure gradient through the ®lm (Hernandez et al. 1986). The permeability coe cient is based on two fundamental mass-transfer parameters: the diŒusion and solubility coe cient. The diŒusion coe cient D is a measure for the rate of penetrant molecules moving through the barrier, in the direction of lower concentration or partial pressure. Pasternak et al. (1970) presented an equation to determine the diŒusion coe cient (D) from the unsteady state portion of the permeation curve:

Table 2 presents the absorptions of each individual ¯avour compound by PP and the in¯uence on the oxygen permeability up to 8 h of exposure. Limonene was showed to have the highest a nity for PP up to a maximum of 15.76 mg g 1 PP, followed by decanal with 8.46 mg g 1 PP, hexyl acetate with 4.56 mg g 1 PP and nonanone with 4.44 mg g 1 PP. Table 2 shows that PPP (O2 ) increased with increasing concentrations of absorbed ¯avour compounds in the polymer. A signi®cant …p < 0:001† linear relationship between oxygen permeability and ¯avour absorption

Flavour absorption, oxygen permeation and plastics food packaging


Table 2. Initial absorptiona (mg g (10 18 m3 m m 2 s Pa) at 25°C.

1

307

PP) of individual ¯avour compounds by PP and the eŒect on O 2 permeability

Exposure time (h)

Limonene

P (O2 )

Decanal

P (O2 )

Hexyl acetate

P (O2 )

Nonanone

P (O2 )

0 1 2 3 4 5 6 7 8

0.00 2.92 6.60 9.50 11.28 11.22 12.72 13.25 15.76

2.18 2.41 2.67 3.00 3.19 3.28 3.40 3.55 3.79

0.00 2.40 4.15 5.20 6.22 7.01 7.49 8.05 8.46

2.18 2.26 2.36 2.40 2.45 2.56 2.56 2.60 2.62

0.00 2.36 3.46 4.05 4.29 4.43 4.44 4.56 4.49

2.18 2.29 2.53 2.61 2.64 2.75 NDb 2.77 2.77

0.00 0.78 1.56 2.37 3.01 3.84 4.17 4.35 4.44

2.18 2.08 2.26 2.35 2.47 2.51 2.40 2.64 2.63

Slope (x, y) Intercept (x, y) R2 …x; y† Level of signi®cance …d:f: ˆ n 2† a b

0.1036 2.0934 0.9808 p < 0:001

0.0541 2.1473 0.9691 p < 0:001

0.1335 2.1055 0.8918 p < 0:001

0.1071 2.1005 0.8312 p < 0:001

Average of two replicates; RSD