PACKAGING EVALUATION FOR HIGH-PRESSURE HIGHTEMPERATURE STERILIZATION OF SHELF-STABLE FOODS

TATIANA KOUTCHMA1,7, YOONSEOK SONG2, ILONA SETIKAITE1,3, PABLO JULIANO4,5, GUSTAVO V. BARBOSA-CNOVAS4, C. PATRICK DUNNE6 and EDUARDO PATAZCA1
1

Illinois Institute of Technology Summit-Agro, IL, 60501

2 Food and Drug Administration National Center for Food Safety and Technology Summit-Agro, IL, 60501 3

Quaker-Tropicana-Gatorade PepsiCo Barrington, IL

Department of Biological Systems Engineering Washington State University Pullman, WA 99164-6120 Innovative Foods Centre Food Science Australia Werribee, VIC, 3030, Australia
6 US Army Research Development & Engineering Command Natick, MA 01760 5

Accepted for Publication July 8, 2008

ABSTRACT The integrity of exible packages during high-pressure (HP) sterilization is of critical importance to the safety and shelf life of food products. For HP-sterilization, packaged products need to be preheated to a target temperature before HP processing. Preheating efciency can be affected by the packaging material utilized. The objectives were to quantify the impact of packaging materials on the rate of heat penetration into foods during preheating, and to evaluate the effects of preheating and HP processing (at 688 MPa and 121C) on package integrity, oxygen permeability and mechanical
7

Corresponding author. Agriculture and Agri-Food Canada, 93 Stone Road West, Guelph, ON, N1G 5C9 Canada. TEL: 519-780-8083; FAX: 519-829-2600; EMAIL: koutchmat@agr.gc.ca

Journal of Food Process Engineering 33 (2010) 10971114. All Rights Reserved. Copyright the Authors Journal Compilation 2009 Wiley Periodicals, Inc. DOI: 10.1111/j.1745-4530.2008.00328.x

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properties for commercially available packaging materials. Commercial scrambled egg patties were vacuum-sealed in pouches. Four plastic-laminated materials (nylon/coextruded ethylene-vinyl alcohol, nylon/polypropylene [PP], polyethylene terephthalate [PET]/aluminum oxide/casted PP [CPP] and PET/polyethylene) and two aluminum foil-laminated pouches (PET/ aluminum [Al]/CPP and nylon/Al/PP) were tested. Selected packaging materials also were evaluated after thermal retort (TR) treatment and HP low temperature processing. The results demonstrated that foil-laminated materials provided shorter preheating time than thinner polymeric materials. HP treatment at high temperatures (HP-HT) increased seal strength of foillaminated pouches. However, the HP-HT process did not signicantly contribute to changes in seal strength of plastic-laminated pouches. It was found that the HP-HT process altered the oxygen barrier of the composite packaging materials. However, the increase in permeability observed during the HP-HT process was attributed to thermal damage occurring during preheating. TR processing increased oxygen permeability to a higher extent than HP-HT processing. It was concluded that the selected packaging materials could provide the required oxygen barrier for HP-HT treated shelf-stable foods.

PRACTICAL APPLICATIONS Research reporting the effects of high-pressure/high-temperature (HPHT) processing on packaging materials is limited. The results of this study demonstrated that foil-laminated materials provided shorter preheating time prior to HP-HT treatment than thinner polymeric materials. In addition, it was shown that foil-laminated packages are a viable option for packaging materials for use in HP-HT processing of shelf-stable low-acid food (LAF) products in terms of their overall appearance, seal strength and oxygen permeability rate. Among plastic pouches, HP-HT treatment showed the lowest impact on EVOH packages. This study is useful for not only researchers who are working in the area of HP processing of shelf stable LAF, but also in research and development of HP treatment of extended shelf life foods. The results may be successfully used in the design and performance evaluation of new laminated packaging materials suitable for HP treatments at high and moderate temperatures. INTRODUCTION The most popular processing method currently used in the food industry to produce shelf-stable sterilized low-acid foods (LAF) is thermal retorting (TR). A promising alternative to this conventional sterilization method is high-

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pressure high-temperature (HP-HT) processing. This technique provides fast heating and fast cooling due to decompression and hydrostatic compression, respectively, of the preheated food package. Even though high-pressure lowtemperature (HP-LT) processing is gaining commercial recognition worldwide as a pasteurization method in offering retention of nutrients and sensory characteristics, HP treatment still requires thermal assistance to achieve product sterilization (Barbosa-Cnovas and Juliano 2008). In HP-HT sterilization, the volumetric temperature increase above 100C at pressures above 600 MPa for holding times of 35 min, compared to 2040 min in retort processing, has been shown to achieve microbial spore inactivation (Koutchma et al. 2005). Therefore, the reduced exposure of the product to high temperatures can produce shelf stable products with sensory characteristics not achievable by conventional retort processing (Matser et al. 2004; Juliano et al. 2007). In general, prior to treatment with HP, food products are prepackaged in exible packaging materials and placed in a pressure vessel lled with a pressure-transmitting uid (normally water). For HP-HT sterilization, exible packages containing food are preheated to target initial temperatures before the HP-HT processing stage, which may further damage the packaging materials. The integrity of heat-treated packaging materials during and after HP processing is, therefore, of critical importance to the safety and shelf life of the food product. Several authors have reported the effects of HP processing on the physical and barrier properties of several laminate packaging materials. However, results of this published research mainly concern HP processing at low (10 30C) and moderate temperatures (4060C), and pressures ranging from 50 to 800 MPa and holding times of 530 min (Caner et al. 2004; Le Bail et al. 2006). Fradin et al. (1998) evaluated two multilayered materials, low-density polyethylene (LDPE)/ethylene-vinyl acetate (EVA)/ethylene-vinyl alcohol (EVOH)/EVA/LDPE and polyethylene terephthalate (PET)/aluminum (Al)/ polypropylene (PP). They reported no change in mechanical strength of the materials after HP thawing of a model food at 200 MPa and 1545 min holding time, although their permeabilities to oxygen and water vapor were slightly reduced. Other authors reported that water vapor and oxygen permeabilities of laminated plastic materials, such as PP/EVOH/PP, oriented PP/polyvinyl alcohol and OPP/casted PP (CPP), were not signicantly affected by HP at 400 and 600 MPa, maximum holding time 10 min, and initial temperatures 2040C (Masuda et al. 1992; Ochiai and Nakagawa 1992; Ozen and Floros 2001). Results from Le Bail et al. (2006) also indicated that HP processing up to 600 MPa, at holding time 10 min and initial temperature 10C, minimally affected the mechanical strength and barrier properties of seven different plastic materials tested. However, barrier properties of metal-

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containing lm structures (Al) were greatly affected, as well as to a lesser degree, their mechanical properties even at low and moderate temperatures (Caner et al. 2004). Blisters and ruptures in metal layers were observed after HP processing, which may be attributed to different compressibility and elasticity of metal and polymer layers. Research reporting the effects of HP-HT processing on packaging materials is limited. Schawecker et al. (2002) observed delamination between PP and Al layers in meal-ready-to-eat (MRE) type pouches processed at 90C for 10 min at pressures of 200 MPa and above. Lopez-Rubio et al. (2005) carried out HP processing at 800 MPa and 75.8C along with sterilization experiments in the retort at 121C using EVOH-based packaging materials. The results showed that HP had only a minor, although detectable, effect on the packaging materials, especially compared with the detrimental effects of a TR process. The current industrial requirement for HP sterilization is that the food product temperature build-up due to compression should reach 121C (Koutchma et al. 2005; Barbosa-Cnovas and Juliano 2008). Since the temperature of the product can rise 35C per 100 MPa due to compressive heating (Ting et al. 2002), the initial temperature of the product should be in the range 8795C, depending on the thermal insulation within the HP chamber. Furthermore, the preheating step, to reach the target initial temperature of the prelled pouches, must be as fast as possible to achieve the industrial benets of HP sterilization. Among the critical factors that can affect heat penetration rate into the packaged product, the heat transfer properties of the pouch materials play an important role (Barbosa-Cnovas and Juliano 2008) and need to be characterized. Little has been reported on the heat penetration of packaging materials suitable for HP-HT treatment processes during the package preheating step. In addition, few studies have been published on the effects of preheating on packaging integrity and barrier properties before and after HP-HT processing. Even though numerous barrier materials are used in the food industry, only a few are able to survive HP-HT application (namely, nylon, EVOH, PET, PP, aluminum oxide [AlOx] coating and Al or metalized layer). Several multilayered lms produced from these materials are commercially available and should be characterized and evaluated for suitability to the HT-HP processing. There are, however, very few studies available that report the integrity and barrier properties of individual and multilayered composite lms after preheating and HP-HT processing. The objectives of this study were (1) to quantify the impact of packaging materials on the rate of heat penetration into foods during preheating and HP processing phases; and (2) to evaluate the effects of preheating and subsequent HP-HT processing at 688 MPa and 121C on package integrity, including oxygen permeability and mechanical properties for selected commercially

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available packaging materials. The effects of HP-LT processing at 600 MPa and 5C and TR treatments at 121C on the integrity of these packaging materials were also compared and reported.

MATERIALS AND METHODS Packaging Materials The plastic-laminated packaging materials tested during this study were biaxial nylon/coextruded EVOH (referred to as EVOH; Alcan, Minneapolis, MN), nylon/PP (referred to as PP; The Pyramid Group, La Habra, CA), PET/AlOx/CPP (referred to as AlOx; Toppan Co, Japan) and PET/ polyethylene (referred to as PE; Ampac Flexibles Corporation, Minneapolis, MN). The aluminum foil-laminated pouches included PET/Al/CPP (referred to as P-Al; Smurt-Stone, Schaumburg, IL) and nylon/Al/PP (referred to as N-Al; The Pyramid Group, La Habra, CA). Food Samples Commercial scrambled egg patties with a round and rectangular shape (Michael Foods Egg Products Co., Gaylord, MN) were used for this study. The average mass of each egg patty was 42.5 7.1 g. Handling and shipping procedure of the egg patties was performed in an industrial setting, where patties were stored in a frozen state before HP treatment. Frozen samples from a single lot were received and stored at -30C. Each patty was placed in a pouch (89 mm 89 mm) that was sealed using an impulse sealer (Model A300/41/ 42, Multivac, Kansas City, MO) with or without vacuum at 10 MPa. High-Pressure Processing HP treatments of packed egg patties were carried out using two pilot scale 35 L HP units, the Quintus Press QFP 35LS and QFP 35L (Avure Technologies, Kent, WA). The pressure medium in both units was water. The QFP 35LS unit was designed for operations up to 690 MPa and 130C. The system consisted of multiple subsystems: a preheating tank; a cooling tank; a wire-wound vessel; low-pressure lled systems; high-pressure pumps; and control systems. Four thermocouples (K-type, Omega Engineering Inc., Stamford, CT) were used to measure the temperatures of the pressure medium and food sample. The QFP 35L unit, with only one thermocouple installed to measure pressure medium temperature, was designed for operations at ambient temperatures and maximum pressures of 600 MPa.

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HP- HT T >100 f Temperature (deg C) T T >70 i dc

HP -LT T f T c dc

T o

o HP -HT

680 600 Pressure (MPa)

H P- L T

Preheat
8 - 10 min

CUT
2 min

Holding
3 min

CDT
1 min

Process time ( min)

FIG. 1. THE TEMPERATURE AND PRESSURE HISTORIES DURING HIGH-PRESSURE STERILIZATION (HP-HT, SOLID LINE) AND PASTEURIZATION (HP-LT, DOTTED LINE) PROCESSES. SYMBOLS REPRESENT PRODUCT TEMPERATURES AT INITIAL (To), AFTER PREHEAT (Ti), DURING HP (Tf), AFTER DECOMPRESSION (Tdc) AND AFTER COOLING (Tc) PROCESSES HP-HT, high-pressure high-temperature; HP-LT, high-pressure low-temperature processing; CUT, come-up time; CDT, come-down time.

The typical HP sterilization process cycle includes preheating time, come-up time, holding time and come-down time followed by cooling time. Figure 1 schematically shows temperature and pressure proles during HP-HT sterilization and HP-LT pasteurization processes. Table 1 summarizes nal temperatures of packaged food samples at the critical control points for HP-HT (688 MPa) and HP-LT processes (600 MPa). For the HP-HT process, the food samples were rst preheated to 55C in a water bath. For the second preheating stage, the samples held inside a polymeric carrier were placed into the preheating tank until reaching the target temperature of 88C inside the samples; then the carrier was placed inside the QFP 35LS unit. The initial

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TABLE 1. TEMPERATURES OF PACKAGED PRODUCTS AT CRITICAL CONTROL POINTS Critical control points Product temperatures (C) High-pressure high-temperature (688 MPa) Initial (To) After preheat (Ti) Final high-pressure process (Tf) After decompression (Tdc) After cooling (Tc) 50 88 123 87 10 5* 2 2 2 High-pressure low-temperature (600 MPa) 5 24 6 1 1 1

* Samples were placed in a water bath at 55C to equilibrate prior to being placed in the polymeric carrier.

temperature of the pressure vessel walls and compression uid was 90C, which enabled achieving the nal sterilization process temperature of at least 121C at 688 MPa. For the HP-LT process, experiments were carried out using the QFP 35L unit at an initial vessel process temperature of 25C at 600 MPa. After HP treatments, samples were immediately cooled and stored at ambient conditions for further tests. Preheating The impact of packaging materials on heat penetration rate during the preheating phase was studied by using a preheating tank at boiling temperature (100C). The EVOH, AlOx and P-Al pouches along with inserted thermocouples were lled with egg patties and sealed at 10 mbar vacuum. Temperature was measured at the geometrical center of individual egg patties using a thermocouple (T-type, Omega Engineering Inc., Stamford, CT) xed in place by a stufng box (Ecklund Harrison Tech., Fort Meyers, FL). Rubber gaskets were inserted to prevent penetration of water into the package. Three replicate pouches for each type were prepared and tested. Initial product temperature was -10C. Time-temperature proles were recorded for each tested pouch until the temperature reached 100C. TR For TR treatment, egg patties were packaged in PP, P-Al and N-Al pouches and processed at 121C for 3 min (Fo = 5.8 min) in a steam retort (Steritort, FMCFood Tech, Madera, CA). Seal Strength Measurement An Instron series 4302 tensile testing machine (Instron Corporation, Canton, MA) equipped with a data acquisition system was used to measure

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seal strength of HP-treated and -untreated pouches. Test specimens (24.5 mm wide and 95 mm long) were cut from the pouches according to the ASTM standard (ASTM F-88 2006). Initial grip separation and cross-head speed were set at 10 cm and 2.54 cm/min, respectively. The seal strength of each specimen was obtained from the maximum peak of the curve. The difference between results for all samples was evaluated using statistical t-tests (a = 0.05), which were done at least in triplicate. Visual Examination All pouches were examined visually for delamination, exing or other retort or high-pressure-induced anomalies. Oxygen Permeability Determination The Mocon 10/50 Oxtran (Mocon Instrument, Minneapolis, MN) was used to measure oxygen permeation rates. The HP-treated, TR-treated and untreated pouches were cut into circular disks, 12.5 cm in diameter, and clamped inside testing chambers. Once equilibrium in the testing cell was reached, the carrier gas N2 containing 3% H2 was routed through the lower half of the chamber. Oxygen was fed through the upper test chamber. Once oxygen permeated through a specimen, it was picked up by the carrier gas and measured by a sensor to determine oxygen permeation rate of the specimen. Oxygen Indicator Dye Test A unique oxygen indicator gel system was designed to measure the incoming of oxygen into plastic pouches. Transparent plastic-laminated pouches PE, PP, EVOH and AlOx were used for the test. Both 2,6dichloroindophenole (IP) and ascorbic acid (AA) standard solutions were prepared according to the AOAC test for ascorbic acid (AOAC 43.064 1984). The IP standard solution was titrated against an AA standard solution for exact measurement of IP concentration. When added to the IP solution, AA reduced the color of the blue IP to a light yellow solution. The mixture was combined with 2% agar, stirred and boiled to gelatinize, tempered to around 50C in a water bath and then poured into a pouch for testing. The package was squeezed to remove all headspace gas and then sealed using a vacuum sealer. After preheating and completing the HP-HT process, sample pouches were stored at room temperature and visually monitored daily up to 60 days. Data Analysis Microsoft Excel 7.0 (Microsoft Corporation, Redmond, WA) and JMP statistical software (SAS, Cary, NC) were used to perform mathematical and statistical analysis.

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RESULTS AND DISCUSSION Effect of Pouch Material on Preheating Time To evaluate the effect of pouch materials on heat penetration rate, timetemperature curves were collected during the preheating phase. Temperature proles of the geometrical center of egg patties packed in P-Al, EVOH and AlOx pouches at respective thickness of 6.0, 5.5 and 4.0 mL are presented in Fig. 2. Based on the data, heat penetration curves were constructed in a semi log scale to derive the heating rate index fh or time needed for a heat penetration curve to cross one log cycle as -1/slope (see Fig. 3). Heating lag factor jh was also calculated as:

(T T ) jh = w a Tw To

(1)

where Tw is water bath temperature, Ta is apparent initial temperature needed to yield a straight line and To is initial temperature of foods. After heating rate parameters were determined, the time required to reach the target preheat temperature of 90C (tB) was calculated:

j (T T ) t B = fh log h w o Tw Tb
110 100 90 80
Tw T2 T1 T3 AlOx (T1) P-Al (T2) EVOH (T3) Boiling water Tw

(2)

Temperature (C)

70 60 50 40 30 20 10 0 -10 0 -20

200

400

600

800

1000

1200

1400

Time (s)
FIG. 2. TIME-TEMPERATURE PROFILES AT THE GEOMETRICAL CENTER OF EGG PATTIES PACKED IN RETORTABLE POUCHES

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1.9 Lo g(Tw-T1 )=-0.002x + 2.459 AlOx

Log 10 (Temperature)

1.4

Log (Tw-T2) = -0.002x + 2.158 P-Al

Log (Tw-T3) =-0.002x + 2.317 EVOH

0.9 250

300

350

400

450

500

550

Time (s)
FIG. 3. HEAT PENETRATION CURVES FOR TESTED POUCHES WITH EGG PATTIES

TABLE 2. HEATING RATE PARAMETERS AND TIME TO REACH TARGET PREHEAT TEMPERATURES IN EGG PATTIES PACKED IN P-Al, EVOH AND AlOx POUCHES Pouch Heating rate fh , s P-Al EVOH AlOx 455 500 500 Lag factor jh 1.3 2.5 1.8 Heating time to 90C min 8.8 12.2 11.0

P-Al, aluminum foil-laminated pouch that includes PET/Al/CPP; EVOH, ethylene-vinyl alcohol; ALOx, aluminum oxide.

The results in Table 2 demonstrated that egg patties packed in the foillaminated P-Al pouch had the lowest heating rate index (455 s), compared with 500 s for plastic-laminated EVOH and AlOx pouches, even though the P-Al pouch was thicker than the others tested. A higher heating rate in P-Al pouches may be attributed to the high heat conductivity of aluminum layer in the pouch. The P-Al pouch also showed the lowest heating lag factor (1.3), followed by the AlOx pouch (1.8) and EVOH pouch (2.5). As a result, the heating time needed to achieve the preheat target temperature of 90C in egg patties was shortest for the P-Al pouch. Table 2 shows that heating times required to reach 90C for EVOH, AlOx and P-Al pouches were 12.2, 11.0 and

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8.8 s, respectively. Since the preheat time can determine the quality of food after the HP-HT sterilization process, a highly thermal conductive material such as P-Al is more suitable than the other two and can thereby assist in reducing thermal impact by means of faster preheating. Overall Package Integrity after HP-HT In general, experiments showed that all packages behaved very well under high pressure, up to 688 MPa, showing no signs of leakage or critical damage to material surfaces and seals. However, some sporadic blisters (less than 3 mm in size) were found on most of the exterior package walls of several PP, P-Al and N-Al pouches after HP-HT treatments at 688 MPa and 121C for 3 min. Neither foil-laminated nor PP pouches lost their initial appearance and physical integrity after retort treatment. EVOH pouches, intended only for hot ll, dramatically changed in appearance from a uniform to a rugged surface after high heat exposure, and thus further TR tests using the EVOH pouch were not conducted. Seal Strength Effect of HP-HT on Seal Strength. Sealing is a critical point in highpressure processing of exible food pouches. Seal strength must be maintained throughout processing to achieve good package integrity without leakage. Effects of HP-HT treatments at 688 MPa and 121C on seal strength were evaluated for vacuum sealed EVOH, AlOx, PP, P-Al and N-Al pouches; the results are summarized in Fig. 4. In general, the AlOx pouch showed the lowest seal strength among the pouches tested. Statistical analysis of the data showed signicant differences in seal strength for foil-laminated pouches before and after the HP-HT treatment coupled with preheating at 90C (P < 0.05). The seal strengths of P-Al and N-Al pouches increased from 186 to 244 kgf/mm and from 360 to 630 kgf/mm, respectively. Lambert et al. (2000) reported that seal strength of a foil-laminated pouch with a structure of PET/ Al/PP did not change after HP processing at 600 MPa and 20C. The discrepancy may result from different temperatures experienced by the pouches during high-pressure processing. Results in foil-laminated pouches indicate that high temperature during the HP-HT processing may play a signicant role in increasing seal strength, which will contribute to the overall enhancement of package seal integrity. On the other hand, as shown in Fig. 4, there were no signicant changes in seal strength for plastic-laminated EVOH, AlOx and PP pouches after HP-HT treatments (P < 0.05). Dobias et al. (2004) observed that seal strengths of plastic-laminated lms, such as polyamide foil extruded by polyethylene

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1000

Seal strength at break (kgf/mm)

800

Control HP-HT

600

400

200

0
EVOH AlOx PP P-Al N-Al

Pouch types

FIG. 4. SEAL STRENGTHS OF VARIOUS VACUUM-SEALED POUCHES BEFORE AND AFTER HP-HT TREATMENTS HP-HT, high-pressure high-temperature.

foil (PA/PE) and PE/PA/EVOH/PE laminates, were not signicantly affected by HP processing at 600 MPa and 20C. The same conclusion was reached for 16 different structures of plastic-laminated pouches after HP treatments at 200500 MPa and 20C (Lambert et al. 2000). Therefore, it can be concluded that high-pressure processing at elevated temperature does not signicantly contribute to the changes of seal strength in plastic-laminated pouches. Effect of Pouch Vacuum Level on Seal Strength after HP-HT and TR Treatments. The seal strengths of PP, P-Al and N-Al pouches, sealed at 0 and 10 mbar vacuum after HP-HT process at 688 MPa and 121C for 3 min, were compared (Fig. 5) with those after TR at the identical temperature of 121C and holding time of 3 min. In general, the HP-HT processed pouches showed greater seal strengths than the corresponding pouches treated under TR processing. The results imply that there was a signicant effect due to high pressure (or in combination with high temperature) on seal strength of the plastic and foil-laminated pouches. No correlation was found between the vacuum levels used and the seal strength obtained for all pouch samples, regardless of the process (HT-HP or TR) applied. Statistical analysis of the results also showed that seal strengths of foil-laminated P-Al and N-Al pouches were not affected by the retort treatment (P < 0.05). The TR process,

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1000

Seal strength at break (kgf/mm)

800

Control HP-HT/ vacuum HP-HT/ no vacuum TR - vacuum TR - no vacuum

600

400

200

PP

P-Al

N-Al

Pouch types

FIG. 5. COMPARISON OF EFFECTS OF HP-HT AND TR PROCESSES ON SEAL STRENGTHS FOR PP, P-Al AND N-Al POUCHES SEALED AT 0 AND 10 MBAR VACUUM PP, polypropylene; P-Al, aluminum foil-laminated pouch that includes PET/Al/CPP; N-Al, aluminum foil-laminated pouch that includes nylon/Al/PP.

however, signicantly reduced the seal strength for plastic-laminated PP pouches (P < 0.05). The comparable results were found by Wooddell (2006) and Roop et al. (1983), where TR processing decreased the seal strengths of polymer-laminated retortable pouches with structures PET/CPP and nylon/ CPP, but had no effect on seal strength of foil-laminated MRE pouches. Effect of Preheating on Seal Strength during HP-HT Process. The effect of the preheating operation up to 90C on the seal strength was determined for EVOH, AlOx and P-Al pouches; results are summarized in Fig. 6. Preheating affected the seal strength of the EVOH pouch (P < 0.05) but not the seal strength of the AlOx and P-Al pouches. The results were in agreement with the previous data in Fig. 5, where seal strengths of foil-laminated P-Al and N-Al pouches were not affected by the TR process, but the seal strength of plastic-laminated PP pouches was signicantly reduced. In the EVOH pouch, seal strength was recovered after subsequent HP-HT process at 688 MPa and 121C for 3 min, resulting in no signicant differences from the untreated control. For the P-Al sample, however, a signicant increase in seal strength was observed after the HP-HT process, which contributed to overall increase in seal strengths compared to the control.

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600

Control Seal strength at break (kgf/mm) Preheating

400

HP-HT

200

0
EVOH AlOx P-Al

Pouch types

FIG. 6. EFFECT OF HP-HT PROCESSING AND PREHEATING OPERATIONS ON SEAL STRENGTHS OF PP, P-Al AND N-Al POUCHES SEALED AT 10 MBAR VACUUM HP-HT, high-pressure high-temperature; PP, polypropylene; P-Al, aluminum foil-laminated pouch that includes PET/Al/CPP; N-Al, aluminum foil-laminated pouch that includes nylon/Al/PP.

Oxygen Permeability Effects of preheating and subsequent HP-HT processing on oxygen barrier properties were evaluated for all pouches. The oxygen transmission rate (OTR) values for the controls (untreated), preheated, HP-HT treated and specic retort treated and HP-LT treated samples are summarized in Table 3. Effect of Preheating and HP-HT Processing. In general, preheating signicantly increased OTR values for all the sample pouches tested. The AlOx pouch in Table 3 showed the greatest loss of oxygen barrier property by 369 times after the preheating, followed by PP, EVOH, P-Al, N-Al and PE samples. After the preheating and subsequent HP-HT process at 688 MPa and 121C for 3 min, there were no further changes in OTR values for EVOH, AlOx and P-Al samples, but a slight increase was observed for N-Al sample. Nondestructive dye tests showed that gel mixtures in AlOx pouches, treated with preheating or subsequent HP-HT process, turned from light yellow to blue after 1 day, while those in EVOH pouches did not change color during the 60-day storage period. The PE pouch showed the highest OTR among all the plastic- and metal-laminated pouches tested. The oxygen barrier in the PE pouch deterio-

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TABLE 3. OXYGEN TRANSMISSION RATES (CC/DAY M2 ATM) OF DIFFERENT SAMPLE POUCHES BEFORE AND AFTER HP-LT, PREHEATING, HP-HT AND TR PROCESSES Pouch PE PP EVOH AlOx P-Al N-Al Control 78.2 1.1 0.05 0.01 0.05 0.01 0.05 0.01 <0.05 <0.05 HP-LT 8.9 0.4 Preheating 109.3 0.78 1.9 18.5 0.32 0.24 1.5 0.15 0.3 0.4 0.15 0.10 HP-HT 25.3 22.6 2.0 19.6 0.40 0.44 0.7 1.5 0.3 0.7 0.15 0.05 TR 0.78 0.51 0.57 0.10 0.10 0.2

HP-LT, high-pressure low-temperature; HP-HT, high-pressure high-temperature; TR, thermal retort treatment; PE, polyethylene; PP, polypropylene; EVOH, ethylene-vinyl alcohol; ALOx, aluminum oxide; P-Al, P-Al, aluminum foil-laminated pouch that includes PET/Al/CPP; N-Al, aluminum foillaminated pouch that includes nylon/Al/PP.

rated by 40% after preheating, but the original value of the OTR was completely recovered and further improved by 200% after HP treatment at 688 MPa and 121C. Oxygen indicator dye tests showed that the gel mixture in PE pouches, both treated and nontreated with preheating or HP-HT process, turned from light yellow to blue even after a 1-day storage at room temperature. It was found that the distribution of color in some pouches was due to the fact that oxidation proceeds from the seal inward toward the middle of the package, probably as a result of the remaining headspace close to the seal area of the package, where compressed air created regions of higher temperature. In the case of the PP sample, the HP-HT process caused an additional increase of 436 times the OTR value obtained after preheating, which resulted in a total 451-fold increase with respect to OTR of the control. As evidenced by some sporadic blisters found in PP pouches after HP-HT treatment, either air trapped in the package or a noncompatible tie-layer could have affected multilayered polymer structures during high-pressure processing (Lambert et al. 2000), which might explain the signicant loss of oxygen barrier property in the PP sample. When processed at HP-LT conditions, the OTR of the PP sample increased 177 times, but the impact was not as signicant as in HP-HT processing. For PP pouches, gel systems treated with HP-HT and HP-LT changed within 2 weeks, but neither control nor preheated samples had changed color until the end of storage experiments. In contrast with HP processing at low and moderate temperature conditions, overall, the HP-HT process coupled with preheating signicantly altered the oxygen barrier properties of the composite packaging materials. In particular, the HP-HT process after preheating played a signicant role in improving or deteriorating oxygen barrier properties for PE, PP and N-Al pouches.

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However, an overall increase in permeance observed during the HP-HT processing was mainly attributed to thermal damage during the preheating stage. Effect of TR Processing. For PP, P-Al and N-Al pouches, there was approximately a 10-fold increase in OTRs over the original values after TR processing (Table 3). The tremendous impact of TR processing on OTR values has been well reported and documented for various multilayered-structured polymer materials. Masuda et al. (1992) investigated the oxygen permeability of PP/EVOH/PP and OP/CPP structures, and found a 230 fold increase in OTR after TR processing at 120C for 30 min. Similar studies (Lopez-Rubio et al. 2005; Wooddell 2006) have conrmed that AlOx/CPP and PP/EVOH/PP lms also lost oxygen barrier properties by 3 and 650 folds, respectively. Table 3 shows that the effects of TR processing on the oxygen barrier property were greater than or the same as the effects of preheating. The OTR values of foil-laminated P-Al and N-Al pouches after preheating were 1.52.4 times less than the OTR values after TR processing. This can be explained by the fact that TR involves more heat and pressure during the process than preheating, and thus the samples during TR processing were subject to more abusive conditions. Overall, the HP-HT process resulted in less oxygen permeability loss in the foil-laminated samples than in the TR process. The result points out that foil-laminated packages are a viable option for packaging materials used in HP-HT processing of shelf-stable LAF products. CONCLUSION Preheating studies on vacuum packed egg patties showed that an aluminum-based pouch was more effective in transferring heat inside the food than a polymeric EVOH or an AlOx-based package. Thus, a metallic-based package can aid in shortening preheating time of the food and provide a product with uniform temperature distribution before pressure treatment, while at the same time, minimize quality degradation due to heating. The experiments proved the inuence of preheating and subsequent HP-HT processing on seal strength and oxygen permeability of selected multilayered packaging lms. The most important effect of HP-HT treatment coupled with preheating was found to be the increasing seal strength of foil-laminated pouches, but the HP-HT process did not signicantly contribute to the changes in seal strength of plastic-laminated pouches. In general, the HP-HT processed pouches showed greater seal strengths than the corresponding pouches treated under preheating or TR processing. It therefore can be concluded that there were signicant effects as a result of high pressure (or, in combination with high temperature) on the seal strengths of plastic- and foil-laminated pouches.

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In general, preheating signicantly increased OTR values for all the sample pouches tested, but there were no signicant further increases in OTR values, except in the PP samples after subsequent HP-HT treatments. Potential structural damage in PP pouches might have caused the tremendous increase in OTR values during the post-preheating HP-HT process. The results imply that the overall increase in permeability observed during HP-HT processing was mainly attributed to thermal damage that occurred during preheating. Overall, the HP-HT process resulted in less loss of oxygen permeability for the foillaminated samples than in the TR process. It therefore can be concluded that foil-laminated packages are an excellent choice for use in HP-HT processing to ensure shelf-stable LAF products.

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