Chapter 6

SECTION III SORPTION BEHAVIOR OF SELECTED ALDEHDYE SCAVENGING AGENTS IN POLY(ETHYLENE TEREPHTHALATE) BLENDS
E.C. SULOFF, J.E. MARCY, B.A. BLAKISTONE, S.E. DUNCAN, T.E. LONG, AND S.F. OKEEFE
Formatted in Accordance with the Journal of Food Science Style Guide.
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Chapter 6: Sorption behavior of selected aldehyde scavenging agents in poly(ethylene terephthalate) blends. ABSTRACT Poly(m-xylylene adipamide) (nylon MXD6), D-sorbitol, and -cyclodextrin aldehyde scavenging agents were blended with poly(ethylene terephthalate) and thermally pressed into films. Films were stored in an acidified aqueous model solution (pH 3.6) containing a 25 M mixture of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and caproaldehyde for 1, 3, 7, and 14 days. The total amount of aldehydes sorbed by films was 2 to 10 times higher for films containing aldehyde scavenging agents then non-blended films. Aldehyde scavenging films demonstrated selective scalping, preferring smaller molecular weight aldehydes to larger aldehydes. Partition coefficients for smaller aldehydes were 3 to 6 times greater for aldehyde scavenging films then control film. INTRODUCTION Research studies investigating the scalping behavior of food packaging materials have mainly focused on how this phenomenon negatively impacts the quality of foods and beverages. Few researchers have addressed how scalping, particularly selective scalping, can be used to improve the flavor profile of food systems. Polymer blends included with an agent that has an affinity for specific compounds can be used to proactively remove deleterious substances in a packaging environment (Del Nobile and others 2002; Hotchkiss 1997; Rooney 2000). The use of such a packaging system can be referred to as active packaging. Food and packaging firms are jointly pursuing new developments in packaging materials, in the form of coatings and blends, in order to extend the quality and shelf-life of foods and beverages. Reynolds (2002) writes that the use of drop-in material, in the form of polymeric additives, that will not require any significant changes in injection-molding of performs or blowing of performs to bottles are likely to emerge in beverage packages in the next two to ten years. The use of polymeric blends in food and beverage containers will likely replace multilayer structures to improve barrier properties and may be tailored to protect product quality
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and extend shelf-life by sensing environmental and product changes. Active packaging in the United States is expected to show a 19% compound annual growth over the next five years (Reynolds 2002). The use of nylons, polyols, and cyclodextrins are described in patent literature to reduce residual acetaldehyde in PET and other polymers (Bobo 1993; Eckert and others 2001; Long and others 2000; Wood and Beaverson 2000). Nylons and other polyamides react with carbonyl compounds by the nucleophillic addition of the free amino group to aldehydes in order to form imines (also known as Schiff bases). nucleophillic addition reaction. D-sorbitol reacts with aldehydes in a reversible An acid catalyst protonates the carbonyl oxygen and
subsequently eliminates water from a hemiacetal intermediate to produce an acetal. Alphacyclodextrin, as well as other cyclodextrins, form inclusion complexes with aldehydes through weak intermolecular forces. Hydrophobic interactions and van der Waals forces are proposed to be the driving forces for the formation of cyclodextrin-aldehyde complexes. In addition, cyclodextrin is believed to form a more stable complex then - or -cyclodextrins for smaller and straight chain guests due to its smaller cavity diameter (Rekharsky and Inoue 1998). The heat treatment of beverages often causes the formation of aldehyde and ketone offflavors. This is particularly true for extended shelf-life (ESL) milk products that undergo ultrahigh temperature (UHT) processing. The formation of aldehyde and ketone off-flavors in UHT processed milk products do not occur immediately, but rather after several weeks of storage (Badings 1991; Shipe and others 1978). 1994; Shibamoto 1980). Lipid oxidation contributes largely to the loss in quality in food products containing lipids and fats. Lipid oxidation in food products can be initiated by a metal catalyst However, hydroperoxides are (autoxidation) or radiant energy (photo-induced oxidation). ESL milk products often exhibit a stale flavor, attributed to the formation of alkanals and methyl ketones during storage (Moio and others
formed by both autoxidation and photo-induced oxidation of fatty acids and are the principle source of off-flavors developed by lipid oxidation. Hydroperoxides are unstable and readily breakdown to form, among other volatiles, aldehydes. The mass transfer of substances from packaging material to a food product is known as migration. The migration of low molecular weight compounds formed during the polymerization, processing, and forming of packaging materials is particularly problematic. For
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example, acetaldehyde is formed in the polyester poly(ethylene terephthalate) (PET) by the thermal decomposition of the ethylene glycol hydroxy terminal group and main chain of the polymer (Ikgarashi and others 1989). The migration of acetaldehyde from PET is well documented and continues to be a problem with this packaging material. An aliphatic series of aldehydes were selected as molecular probes in order to examine the effects of molecular weight, chain length, and solubility on sorption affinity for similar species. In addition, these compounds are readily formed by thermal processing, lipid oxidation, and package migration during the storage of many foods and beverages and have extremely low odor and flavor thresholds. MATERIALS AND METHODS Materials The bulk polymer, PET (Eastpak Polymer 9921W), was supplied by Eastman Chemical Co. (Kingsport, TN). Nylon MXD6 (MXD6-6001) was supplied by Mitsubishi Gas Chemical Co. (New York, NY). D-sorbitol was purchased from Aldrich Chemical Co. (Milwaukee, WI) and -cyclodextrin was supplied by Cerestar (Hammond, IN). Acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and caproaldehyde were purchased from Aldrich Chemical Co. (Milwaukee, WI). Preparation of Polymer Films PET and nylon MXD6 pelletized resin were reduced in size to allow for uniform compounding. Resin pellets were freeze fractured into a fine powder by submerging the pellets in liquid nitrogen for 5 min and grinding them in a Vortec Impact Mill Model M-1 (Vortec Products Co., Long Beach, CA). The freeze fracture process was repeated two additional times in order to obtain particles with a suitable size prior to compounding. D-sorbitol and cyclodextrin were not further reduced in size prior to compounding. Bulk polymer (95) and aldehyde scavenging agents (5) were combined as a dry mixture in 250 g batches. Mixtures were shaken on IKA Model VXR S1 platform shaker (IKA Works, Inc., Wilmington, NC)
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operating at motor setting 1000 for 48 hrs in order to achieve a homogeneous mixture. Mixtures were then dried at 60C overnight in a vacuum oven at reduced pressure. Neat PET and polymer mixtures were then pressed into films using a thermal press. Neat PET and mixtures (5.0 0.1 g) were evenly dispersed on a stainless steel metal frame measuring 10 cm x 10 cm with a thickness of 356 m. Both sides of the stainless steel frame were lined with Kapton film (DuPont, Wilmington, DE) in order to improve the removal of cast film from the metal frame after cooling. The stainless steel frame was then placed between two larger aluminum plates and placed in a PHI Precision Press Model GS 21-J-C-7 (Pasadena Hydraulics, Inc., City of Industry, CA) operating at 270C and 881 KPa. Films were pressed for 90 sec and then immediately submerged in an ice bath. Films were removed from steel frame, dried with a towel, and then cut into strips measuring 2 cm x 7.5 cm. Finally, film strips were placed in a vacuum oven at 30C overnight at reduced pressure. Characteristics of thermally pressed PET films are listed in Table 2. Density Analysis The densities of powdered aldehyde scalping agents and cast films were determined by gas pyconometry (Palacio and others 1999; Sartore and others 2002). Density analysis was performed using Micromeritics AccuPyc 1330 pycnometer (Micromeritics Instrument Company, Norcross, GA) operating at an ambient temperature and using helium as the displacement medium. Thermal Analysis Differential scanning calorimetry (DSC) was used to determine the percent crystallinity of cast films. Percent crystallinity for cast films was determined using a Perkin Elmer Pyris 1 DSC (Perkin Elmer, Inc., Wellesley, MA) equipped with Pyris Software Version 3.81 data acquisition platform. Cast films were analyzed under an ambient atmosphere and a temperature program of 25-200C at 10C/min. Percent crystallinity was calculated based on the area of the crystallization peak on the first heating profile.
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The thermal stability of the aldehyde scavenging agents and cast films was determined by thermal gravimetric analysis (TGA). TGA measurements were made using a TA Instruments HiRes TGA 2950 Thermogravimetric Analyzer (TA Instruments, New Castle, DE) operating under nitrogen and a temperature program of 25-600C at 20C/min. Degradation temperature (Td) was calculated using TA Instruments Thermal Advantage Release 1.0 software. Preparation of Aqueous Model Solutions Stock solutions of molecular probes (0.01 M) were prepared in a cold room, 7 4C, using 0.0001 N HCl (pH = 3.6 0.2) as a solvent. Stock solutions were mechanically stirred for 20 min in tightly stoppered flasks to prevent loss of volatiles. Stock solutions were then diluted 1:40, using 0.0001 N HCl solvent, in a common volumetric flask in order to achieve a mixture containing a concentration of 250 M for each molecular probe. Solution was mechanically stirred for 20 min in a tightly stoppered flask. Preparation of Exposure Vials The weight of each 15 cm2 film strip was recorded and then placed in a 40 mL exposure vial fitted with a Teflon-fluorocarbon-resin lined cap. Precisely 9 mL of 0.001 N HCl solvent and 1 mL of solution containing 250 M concentrations of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and caproaldehyde were added to each exposure vial. Exposure vials were prepared in triplicate in a cold room maintained at 7 4C. Aqueous model solution (pH 3.6) used in exposure vials included 25 M concentrations of aldehydes. Exposure Conditions Exposure vials were placed horizontally in test tube racks allowing test strips to be completely submerged in model solution. Test tube racks were fitted in a Lab-Line Orbit Environ-Shaker Model 3527 (Lab-Line Instruments, Inc., Melrose Park, IL) operating at 250 r.p.m. Exposure vials were gently shaken for 1, 3, 7, and 14 days at an ambient temperature.
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2,4-Dinitrophenylhydrazine Derivatization Procedure for Molecular Probes The 2,4-dinitrophenylhydrazine (DNPH) reagent was prepared daily in multiple 50 mL glass centrifuge tubes. Forty-three mg of 2,4-dinitrophenylhydrazine (30% water w/w) (Aldrich Chemical Co., Milwaukee, WI) was dissolved in 30 mL mixture of hydrochloric acid, water, and acetonitrile (5:11:4). Carbonyl contamination contained within the DNPH reagent was removed by extraction with carbon tetrachloride. Carbon tetrachloride (4 mL) was added to DNPH reagent (30 mL) and was vigorously shaken for 5 min. The mixture was then centrifuged using a Sorvall Refrigerated Superspeed Centrifuge Model RC-5B (DuPont Instruments, Wilmington, De) at 949 G for 20 min in order to separate the phases. Extracted DNPH reagent was used for derivatization reaction. Exposure vials were removed from orbital shaker and chilled to 7 4C after 1, 3, 7, and 14 days. Film strips were quickly removed from molecular probe solution and were rinsed with precisely 1 mL of water. Exposure vials were then immediately capped to avoid loss of volatile aldehyde species. DNPH reagent (5 mL) was then added to exposure vials. Reaction vials were then shaken using a Lab-Line Orbit Environ-Shaker Model 3527 operating at 250 r.p.m. for 5 hrs at ambient temperature. Derivatization reaction conditions within reaction vial were 1.0 M HCl and 2.5 mM DNPH (20 equiv. of total aldehyde concentration). These conditions were found to be optimum for the formation of aldehyde-hydrazine complexes. Vials were then removed from orbital shaker and diluted with 9 mL of acetonitrile to dissolve any aldehyde-hydrazine precipitate formed during the derivatization reaction. Table 3 lists percent yields for conversion of aldehydes to aldehyde-hydrazine complexes by this procedure. High Performance Liquid Chromatography Analysis Diluted samples were analyzed using Varian 9010 Solvent Delivery System (Varian, Inc., Palo Alto, CA) equipped with a Varian Model 9050 Variable Wavelength UV-VIS Detector and Dynamax Autosampler Model AI-200 (Rainin Instrument Co., Woburn, MA). Data acquisition and integration was performed using Varian LC Star System Workstation. analytical column (3.9 mm x 300 mm) (Waters Corp., Milford, MA). Separation of aldehydes was accomplished using Waters Nova-Pak C-18 guard column (3.9 mm x 20 mm) and
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The eluent was pumped at a flow rate of 1 mL/min and the UV detector was operated at 360 nm. The injection volume was 50 L. A gradient elution was followed from 50% (v/v) acetonitrile in water to 100% acetonitrile over a period of 20 min. Quantification of aldehyde species was accomplished using an external standard curve based on peak area. Retention times and detector response factors for molecular probes are listed in Table 2. Experimental Design and Statistical Analysis A split-split-plot design was employed. The experiment included three sub-samples for each set of conditions and was repeated three times in a completely randomized block design. LSD analysis adjusted by Tukey-Kramer procedure was used for separation of treatment means. A significance level of p < 0.05 was established to detect statistical differences. Statistical analysis was performed using SAS release 8.2 software, (SAS Institute, Inc., Cary, NC) (SAS Institute 1999). RESULTS AND DISCUSSION Density and Thermal Analysis of Aldehyde Scavenging Agents and Test Films Density and thermal analysis results for aldehyde scavenging agents and test films are listed in Tables 1 and 2. Nylon MXD6, D-sorbitol and -cyclodextrin aldehyde scavenging agents were determined to have densities of 1.19, 1.48, and 0.55 g/cm3. Although the densities of neat aldehyde scavenging agents varied greatly, the densities of PET films containing these same agents were similar. PET : nylon MXD6, PET : D-sorbitol, and PET : -cyclodextrin were determined to have densities of 1.338, 1.351, and 1.357 g/cm3. Aldehyde scavenging PET films were slightly denser then neat PET films with a density of 1.272 g/cm3. In addition, aldehyde scavenging PET films were more crystalline then neat PET films. The percent crystallinities of PET : nylon MXD6, PET : D-sorbitol, and PET : -cyclodextrin were 19, 19, and 20%. Neat PET films were only 13% crystalline. Baird 1996). Increased crystallinity of PET blends containing immiscible adjuncts have been reported else where (Da Silva and others 2002; Guenther and
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Nylon MXD6, D-sorbitol, and -cyclodextrin are reported to have melting temperatures of 237, 98, and 255C. These same additives showed degradation temperatures of 396, 294, and 304C. Thermal properties of neat aldehyde scavenging agents indicated that they were suitable for use in PET blends requiring a processing temperature of 270C. However, the thermal properties of the aldehyde scavenging agents changed in the presence of PET. Degradation temperatures for D-sorbitol and -cyclodextrin in PET thermally pressed films were 207 and 284C, respectively. The Td of D-sorbitol decreased by more then 87C in the presence of PET. Similar results were found for -cyclodextrin, where the Td decreased by nearly 20C. The Td of nylon MXD6 in thermally pressed film was not able to be determined since its Td temperature is nearly equivalent to the Td of neat PET. The dramatic decrease in thermal stability of D-sorbitol and -cyclodextrin in PET films is difficult to explain. In fact, one would expect neat aldehyde scavenging agents in powdered form to degrade at lower temperatures then when present in PET films. The presence of terephthalic acid or ethylene glycol might contribute to the degradation of D-sorbitol or -cyclodextrin, however, the Td of PET in films blended with those agents did not occur until 415 or 417C. The presence of terephthalic acid and ethylene glycol at temperatures below their Td is unlikely. It is important to note that TGA thermograms for D-sorbitol and -cyclodextrin indicate their presence in thermally pressed PET films. The pressing conditions, 270C at 881 KPa for 90 sec, did not completely degrade these additives. Differences between the time temperature treatment for additives by the thermal press and TGA analysis may explain their presence in the film. Thermally pressed films underwent an instantaneous heat treatment of 270C for 90 sec, whereas the TGA temperature program included a shallow heating rate of 20C/min. 2,4-Dinitrophenylhydrazine Derivatization and HPLC Analysis of Molecular Probes The derivatization of aldehydes by 2,4-dinitrophenylhydrazine followed by their separation by HPLC allowed for precise quantitative measurement of molecular probes at submicromolar levels in the model solution. HPLC analysis of aldehyde-hydrazines offered more precise results and a lower level of detection then was achieved by solvent extraction of test films or solid phase microextraction gas chromatography of model solutions. Table 3 lists the
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percent yield of derivatization with molecular probes, retention times, and detector response factors for molecular probes. Total Aldehyde Concentration in Aqueous Model Solutions The total aldehyde concentration in the aqueous model solution was calculated by taking the sum of all molecular probe concentrations on a particular day. The total aldehyde concentration for the aqueous model solution (control) and model solutions exposed with neat PET, PET : nylon MXD6, PET : D-sorbitol, and PET : -cyclodextrin film strips were 122, 117, 89, 70, and 58 M after one day. These results indicate 4, 27, 43, and 52% reductions in total aldehyde content in model solutions exposed with neat PET, PET : nylon MXD6, PET : Dsorbitol, and PET : -cyclodextrin film when compared to the control solution. Statistical analysis after one day exposure showed differences between control and blended films, but did not show any differences between control and neat PET. Differences were also found between films containing aldehyde scavenging agents. The control model solution and model solutions exposed with neat PET, PET : nylon MXD6, PET : D-sorbitol, and PET : -cyclodextrin films after three days of storage showed total aldehyde concentrations of 117, 99, 77, 60, and 48 M, respectively. These results account for 15, 34, 49, and 59% reductions in total aldehyde content in model solutions exposed to test polymers when compared to control solution. Statistical analysis after three days of exposure showed differences between control and all blended films, as well as neat PET. In addition, each model solution exposed to test films were found to be different from the other three. Total aldehyde concentrations in aqueous model solution control and solutions exposed to test films were nearly identical for seven and fourteen days of storage. Total aldehyde concentration in the aqueous model solution after fourteen days is shown on Figure 1. After seven days of storage, the total aldehyde concentration in control solution and solutions containing neat PET, PET : nylon MXD6, PET : D-sorbitol, and PET : -cyclodextrin were 114, 91, 70, 56, and 45 M. Reductions in total aldehyde content in model solutions after seven days of exposure to test films were calculated to be 20, 39, 51, and 61%. Statistical analysis for seven and fourteen day exposures showed identical results for differences among control and film treatments. Model solutions exposed with neat PET and blended films were statistical different 128
from control solution. Differences between films were found in every instance, except when comparing the PET : D-sorbitol treatment and PET : -cyclodextrin treatment. No difference was found between these two treatments. The concentration of the aqueous model solution control showed minimal degradation during the fourteen day experiment. The initial total aldehyde concentration after day one was 122 M compared to 112 M determined after fourteen days of storage. Similar degradation results have been reported for aldehydes in acidified model solutions (Ayhan and others 2001; Konczal and others 1992; Pieper and others 1992). Sorption Amounts and Rates for Molecular Probes into Test Films The amount and rate of sorption for molecular probes into test films are shown in Figures 2-6. The percentages of acetaldehyde sorbed by neat PET, PET : nylon MXD6, PET : Dsorbitol, and PET : -cyclodextrin test films after fourteen days were 14, 51, 82, and 90%. The rate of sorption of acetaldehyde in blended films was much greater then neat PET. Nearly 95% of acetaldehyde sorption occurred in blended films after one day. The rate of acetaldehyde sorption for neat PET was more gradual. Only 36% of neat PET acetaldehyde sorption occurred after one day. Neat PET, PET : nylon MXD6, PET : D-sorbitol, and PET : -cyclodextrin test films sorbed 10, 39, 56, and 76% of propionaldehyde after fourteen days of exposure. The rate of sorption for propionaldehyde was greater in blended test films then neat PET films. In addition, maximum sorption for propionaldehyde occurred after seven days exposure. days. These results are confusing and only occurred for this molecular probe. Butyraldehyde and valeraldehyde sorption by test films showed similar results to the other molecular probes. Neat PET, PET : nylon MXD6, PET : D-sorbitol, and PET : cyclodextrin test films sorbed 19, 40, 48, and 58% of butyraldehyde after fourteen days of exposure. The percentages of valeraldehyde sorption after fourteen days for these same test films were 27, 36, 40, and 48%. Neat PET, PET : nylon MXD6, PET : D-sorbitol, and PET : cyclodextrin test films sorbed 23, 21, 26, and 23% of caproaldehyde after fourteen days of exposure. However, a decrease in the amount of caproaldehyde sorbed by PET : -cyclodextrin 129 Less propionaldehyde was removed from the aqueous model solution after fourteen days then seven
occurred between seven and fourteen days. Again, the rate of sorption for the molecular probes was greater in blended test films then neat PET film. A relationship between the total amount and rate of molecular probes sorbed by blended test films was established. For instance, blended films sorbed molecular probes with lower molecular weights to greater extent then those with higher molecular weights. PET : nylon MXD6 test films removed nearly 51% of acetaldehyde from the model solution compared to only 21% of caproaldehyde. The differences between sorption of acetaldehyde and caproaldehyde were even more pronounced for PET : D-sorbitol and PET : -cyclodextrin films. The percentages of acetaldehyde sorbed by PET : D-sorbitol and PET : -cyclodextrin were 82 and 90%, compared to 26 and 23% of caproaldehyde sorbed for the same blended films. Molecular probes with lower molecular weights were also found to be removed at a greater rate then higher molecular weight probes in blended films. During the fourteen day exposure period for the blended films, 92, 94, and 93% of acetaldehyde sorption occurred for PET : nylon MXD6, PET : D-sorbitol, and PET : -cyclodextrin after one day exposure. Caproaldehyde sorption occurred at a more gradual rate. Only 19, 58, and 74% of total caproaldehyde sorption occurred after one day exposure for the same films. Trends associated with sorption amount and rate found for blended films were not similar to trends found for neat PET films. In fact, the affect of molecular size on sorption amount for neat PET films were exactly opposite of what was established for blended films. Neat PET films sorbed a greater percentage of higher molecular weight aldehydes then lower molecular weight aldehydes from the model solution. For example, only 14% of acetaldehyde was sorbed after fourteen days of exposure with neat PET film compared to more then 23% sorption of caproaldehyde for the same period. The rate of sorption for molecular probes in neat PET films was much slower then what was seen in blended films. Most molecular probes did not reach equilibrium conditions for sorption until seven days of exposure for neat PET films. Blended films showed near equilibrium conditions after one or three days of exposure. Sorption Affinities of Aldehydes into Test Films Summarized in Figure 7 is the amount (mg) of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and caproaldehyde sorbed per unit volume (dm3) by neat PET,
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PET : nylon MXD6, PET : D-sorbitol, and PET -cyclodextrin after fourteen days of storage. Values obtained from molecular probe sorption, per unit volume of polymeric materials, after fourteen days were used to calculate equilibrium partition coefficients (K) (Table 4). Steady state conditions were established for all molecular probes and test films after fourteen days of exposure. The equilibrium partition coefficient was calculated using equation 1
K=
(Q0 Qt ) / V film
Csol
(1)
where Q0 is the quantity (mg) of the molecular probe in the initial model solution (t=0), Qt is the quantity (mg) of the molecular probe in the model solution after contact (t), Vfilm is the volume of the test film (dm3), and Csol is the concentration (mg/L) in the solution at equilibrium (Leboss and others 1997). Partition coefficients with greater values indicate stronger affinities between aldehydes and test films then partition coefficients with lower values. Equilibrium partition coefficients for aldehydes and blended films were greater then partition coefficients for neat PET films. PET : -cyclodextrin test films showed the highest partition coefficients for aldehdyes, followed by PET : D-sorbitol films and PET : nylon MXD6 films. The only exception to these trends occurred for caproaldehyde. The partition coefficient between caproaldehyde and neat PET films was greater then PET : nylon MXD6 films. In general, partition coefficients between lower molecular weight aldehydes and blended films were greater then partition coefficients for higher molecular weight aldehydes. The opposite was true for neat PET films. PET films showed greater affinities for higher molecular weight probes then lower molecular probes. In another study, (Shimoda and others 1988), the partition coefficient (plastic/solution) increased with molecular weight for a homologous series of saturated aldehydes (hexanal through dodecanal). The number of theoretical scavenging sites found in test films was not a good predictor of sorption capacity for test films. For instance, the theoretical number of free amine groups for nylon MXD6 in each test film is approximately 1.37 x 1018. This approximation was achieved by multiplying the average molecular number, 16,500 g/mol, for nylon MXD6 by the amount present in the test film (3.75 x 10-2 g) and then multiplying that value by 6.022 x 1023 active
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sites/mol. This approximation assumes that only one amine site is available for scavenging per mole of nylon MXD6. The number of molecules for each molecular probe present in each vial is 1.51 x 1017. This approximation was achieved by multiplying the molecular probe concentration (2.50 x 10-5 mol/L) by the volume of model solution in the test vial (0.01 L) and then multiplying this value by 6.022 x 1023 molecules/mol. This attributes to a total of 7.55 x 1017 (1.51 x 1017 x 5 molecular probes) molecules of aldehyde compounds present in each vial. The ratio of theoretical active sites to total aldehyde molecules present in the test vial is 1.81 for the PET : nylon MXD6 film treatment. The number of theoretical scavenging sites for D-sorbitol and cyclodextrin was calculated according to the same procedure discussed for nylon MXD6. However, the stochiometry of D-sorbitol for acetal production by aldehydes is 2:1 and is hypothesized to be approximately 1:1 for -cyclodextrin complexation. The number of theoretical scavenging sites for D-sorbitol and -cyclodextrin films was calculated to be 6.20 x 1019 and 2.32 x 1019. The ratios of theoretical sites to total aldehyde molecules present in test vials for PET : D-sorbitol, and PET : -cyclodextrin treatments are 82.1 and 30.7. PET : Dsorbitol and PET : -cyclodextrin treatments were the most effective in removing aldehydes from the model solution, but nylon MXD6 was the most efficient agent in removing aldehydes from solution. Factors Affecting Sorption Affinity, Capacity, and Rate for Molecular Probes and Test Films The principal variables affecting the sorption process of low molecular weight compounds into polymeric packaging materials include the chemical composition of the packaging material and sorbate molecule, polymer morphology, temperature, initial concentration of the sorbate, sorption capacity of the polymer, and sorbate diffusivity. The dynamics of the sorption process and therefore the time in which to reach equilibrium is controlled by sorbate diffusivity, while the remaining variables determine the specific change in sorbate concentration at equilibrium (Konczal and others 1992). The polarity of a packaging material (sorbent) and molecular probe (sorbate) can dramatically affect their affinities toward one another. In general, sorbents and sorbates with
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similar polarities have higher affinities for one another due the universal rule, like dissolves like. PET is a relatively polar polymer, therefore, it was not surprising that blended PET films sorbed higher molecular weight saturated aldehydes to a lesser extent then lower molecular weight aldehydes. With increasing carbon length, the polarity of saturated aldehydes decreases and consequently, their sorption decreases. The solubility of molecular probes in an aqueous solution is related to their polarity. More soluble compounds are sorbed to a lesser degree by polymers in solution then less soluble compounds (Kwapong and Hotchkiss 1987). Therefore, one would expect that the sorption of a molecular probe with low water solubility, such as caproaldehyde, would be much greater then a probe with very high water solubility, such as acetaldehyde. These results were consistent with findings for neat PET, however, were not found to be true for PET blends, which showed the opposite relationship. The differences found between neat PET and PET blends are likely to be attributed to polymer crystallinity and morphology. Absorption and diffusion of low molecular weight compounds take place in the amorphous area of a polymer (Crank 1968). The crystalline region consists of tightly packed lamellae, which impede the diffusion of molecules. According to this theory, more crystalline polymers show less sorption of small molecular weight compounds then less crystalline polymers. This trend was established for citrus flavor volatiles and aldehydes in polyolefins (Charara and others 1992; Sadler and Braddock 1991; Shimoda and others 1988). The sorption of water molecules in the amorphous region of a polymer has a plasticizing affect on polymers. Differences in the sorption behavior of aldehydes in the blended films were probably due to differences in their polarity and hydrogen bonding with sorbed water in the polymer. Aldehydes, in which hydrogen bonding occurs more readily, are drawn into the amorphous region of the polymer by water vapor. This process brings aldehydes in close proximity to the aldehyde scavenging sites present in the PET blends. Interactions between aldehydes and scavenging agents are stronger than their hydrogen bonding with water molecules. Thus, aldehydes become irreversibly or reversibly attached to a functional group within the polymer matrix. This phenomenon was not shown for neat PET, since no aldehyde scavenging agents impeded the return of aldehyde compounds into solution once equilibrium conditions are established for water sorption in the polymer.
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Finally, polymer morphology may have influenced the sorption behavior of molecular probes. Charara and others (1992) report absorption of orange oils in LDPE causes large fissures and ridges on the polymer surface. He confirmed these findings by the use of scanning electron microscopy (SEM). The creation of uneven surfaces on the polymer surface may promote more extensive adsorption. Kwapong and Hotchkiss (1987) report adsorption to be the dominant sorption mechanism for polymers below their glass transition temperature (Tg). PET materials investigated in this study were well below their Tg. CONCLUSIONS Low molecular weight aldehyde compounds compromise the quality of many food and beverage products. Many of these compounds are degradation products produced from thermal processing, lipid oxidation, and package migration. The addition of nylon MXD6, D-sorbitol, and -cyclodextrin to PET thermally pressed films were shown to effectively remove aldehydes from an aqueous model solution. The sorption amount and rate for aldehydes in aldehyde scavenging films are related to their water solubility and the crystalline structure of the polymer.
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TABLES AND FIGURES INCLUDED FOR PUBLICATION Table 1 - Characteristics of aldehyde scavenging agents used in PET blends Mwa (g / mol) Nylon MXD6 16,500 D-Sorbitol 182 972 -Cyclodextrin a Specifications from manufacturers. b Degradation temperature determined by TGA. Additive Densitya (g / cm3) 1.19 1.48 0.55 Tma (C) 237 98 255-260 Tdb (C) 396 294 304
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Table 2 - Characteristics of thermally pressed PET films Densitya % Thicknessc Tdd (C) (g / cm3) Crystallinityb (mm) Bulke Additivef PET (100) 1.272 13 0.34 413 PET (95): Nylon MXD6 (5) 1.338 19 0.34 406 NDg PET (95) : D-Sorbitol (5) 1.351 19 0.35 415 207 1.357 20 0.33 417 284 PET (95) : -Cyclodextrin (5) a Density measurement by gas pyconometry. b Percent crystallinity measurement by DSC and based on peak area and first heating profile. c Thickness measured by micrometer. d Degradation temperature determined by TGA. e Degradation temperature of bulk PET polymer. f Degradation temperature of aldehyde scalping additive added to bulk polymer. g Td not able to be detected from TGA thermogram. Exposure Material
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Table 3 - Derivatization and HPLC characteristics of molecular probes used in aqueous model solution % DNPH Concentrationa tR b (min) Conversionc (uM) (mg / L) Acetaldehyde 25 1.40 6.89 98 Propionaldehyde 25 1.80 8.86 97 Butyraldehyde 25 2.25 10.67 93 Valeraldehyde 25 2.66 12.52 93 Caproaldehyde 25 3.07 14.25 89 a Initial target concentration for molecular probes in aqueous model solution. b Retention times for aldehyde-hydrazine complexes. c Percent aldehyde-hydrazine complex formed from derivatization procedure. d Relative molar response factor for UV-Vis detector at 360 nm. Molecular Probe Response Factor 292 259 287 267 316
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Aqueous Model Solution
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
PET : Alpha-Cyclodextrin
140 120 100 80 60 40 20 0

a 112 b 91 c 70 d 55
Total Aldehyde Concentration ( M)
d 43
Exposure Material
Figure 1 Total aldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 14 days.
a
Different letters represent statistical differences among exposure materials at p < 0.05.
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PET
PET : Nylon MXD6
PET : D-Sorbitol
PET : Alpha Cyclodextrin
100 80 60 40 20 0 0 2 4
Percent Sorption
Time (days)
10
12
14
Figure 2 Sorption of acetaldehyde by neat PET and aldehyde scavenging PET films in aqueous model solutions.
139
PET
PET : Nylon MXD6
PET : D-Sorbitol
100 80 60 40 20 0 0 2 4
Percent Sorption
Time (days)
10
12
14
Figure 3 Sorption of propionaldehyde by neat PET and aldehyde scavenging PET films in aqueous model solutions.
140
PET
PET : Nylon MXD6
PET : D-Sorbitol
100 80 60 40 20 0 0 2 4
Percent Sorption
Time (days)
10
12
14
Figure 4 Sorption of butyraldehyde by neat PET and aldehyde scavenging PET films in aqueous model solutions.
141
PET
PET : Nylon MXD6
PET : D-Sorbitol
100 80 60 40 20 0 0 2 4
Percent Sorption
Time (days)
10
12
14
Figure 5 Sorption of valeraldehyde by neat PET and aldehyde scavenging PET films in aqueous model solutions.
142
PET
PET : Nylon MXD6
PET : D-Sorbitol
100 80 60 40 20 0 0 2 4
Percent Sorption
Time (days)
10
12
14
Figure 6 Sorption of caproaldehyde by neat PET and aldehyde scavenging PET films in aqueous model solutions.
143
Acetaldehyde 30 25 20 15 10 5 0
PET
Propionaldehyde
Butyraldehyde
Valeraldehyde
Caproaldehyde
Sorption (mg probe / dm3 polymer)
PET : Nylon MXD6
PET : D-Sorbitol
Exposure Material
Figure 7 Sorption of molecular probes per unit volume of neat PET and aldehyde scavenging PET films in aqueous model solutions after 14 days of exposure.
144
Table 4 Partition coefficients for molecular probes after 14 days of contact with neat PET and aldehyde scavenging PET films in aqueous model solutions Contact Material PET PET : Nylon MXD6 PET : D-Sorbitol PET : -Cyclodextrin Acetaldehyde (K) 234 892 1485 1616 Propionaldehyde (K) 162 676 1007 1357 Butyraldehyde (K) 328 698 863 1045 Valeraldehyde (K) 454 621 717 865
Caproaldehyde (K) 382 367 465 587
145
REFERENCES Ayhan Z, Yeom HW, Zhang QH, Min DB. 2001. Flavor, color, and vitamin C retention of pulsed electric field processed orange juice in different packaging materials. J Agric Food Chem 49:669-674. Badings HT. 1991. Milk. In: Maarse H, editor. Volatile Compounds in Foods and Beverages. New York: Marcel Dekker. p. 91-106. Bobo WS, inventor; The Valspar Corporation, assignee. 1993 January 5. Interior can coating compositions containing cyclodextrins. U.S. patent 5,177,129. Charara ZN, Williams JW, Schimidt RH, Marshall MR. 1992. Orange flavor absorption into various polymeric packaging materials. J Food Sci 57:963-972. Crank J. 1968. Methods of measurement. In: Crank J, Park GS, editors. Diffusion in Polymers. New York: Academic Press. p. 1-39. Da Silva LB, Marinelli AL, Ruvolo-Filho A, Bretas RES. 2002. Blends of a bottle-grade polyethylene terephthalate copolymer with a liquid crystalline polymer. Part II. Thermal and transport properties. Polym Eng Sci 42:1694-1709. Del Nobile MA, Buonocore GG, Fava P, Piergiovanni L. 2002. Modeling of hexanal sorption kinetic in an aldehydes scavenging film intended for food packaging applications. J Food Sci 67:2687-2691. Eckert R, Sela M, Munjal S, Nagel M, Voerckel V,Wiegner J-P, inventors; Dow Chemical Co., assignee. 2001 January 4. Extruded products from polyethylene terephthalate with reduced acetaldehyde content and process of their production. U.S. patent 0100724. Fazzalari FA. 1978. Compilation of Odor and Taste Threshold Values Data. American Society for Testing and Materials, Baltimore, MD. Green DW, Maloney JO. 1997. Perry's Chemical Engineers' Handbook, 7th ed. McGraw-Hill Companies, Inc., New York. Guenther GK, Baird DG. 1996. An evaluation of the Doi-Ohta theory for an immiscible polymer blend. J Rheol 40:1-20. Hotchkiss JH. 1997. Food-packaging interactions influencing quality and safety. Food Addit Contam 14:601-607.
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Ikgarashi R, Watanabe Y, Hirata S, inventors; Toyo Seikan Kaisha, Ltd., assignee. 1989 June 6. Thermoplastic polyester composition having improved flavor-retaining property and vessel formed therefrom. U.S. patent 4,837,115. Konczal JB, Harte BR, Hoojjat P, Giacin JR. 1992. Apple juice flavor compound sorption by sealant films. J Food Sci 57:967-972. Kwapong OY, Hotchkiss JH. 1987. Comparative sorption of aroma compounds by polyethylene and ionomer food-contact plastics. J Food Sci 52:761-785. Leboss R, Ducruet V, Feigenbaum A. 1997. Interactions between reactive aroma compounds from model citrus juice with polypropylene packaging film. J Agric Food Chem 45:28362842. Long TE, Bagrodia S, Moreau A, Duccase V, inventors; Eastman Chemical Company, assignee. 2000 March 28. Process for improving the flavor retaining property of polyester/polyamide blend containers for ozonated water. U.S. patent 6,042,908. Moio L, Etievant P, Langlois D, Dekimpe J, Addeo F. 1994. Detection of powerful odorants in heated milk by use of extract dilution sniffing analysis. J Dairy Res 61:385-394. Palacio L, Pradanos P, Calvo JI, Hernandez A. 1999. Porosity measurements by a gas penetration method and other techniques applied to membrane characterization. Thin Solid Films 348:22-29. Pieper G, Borgudd L, Ackermann P, Fellers P. 1992. Absorption of aroma volatiles of orange juice into laminated carton packages did not affect sensory quality. J Food Sci 57:14081411. Rekharsky MV, Inoue Y. 1998. Complexation thermodynamics of cyclodextrins. Chem Rev 98:1875-1917. Reynolds P. 2002. Technology to take us forward. Packag World 9:170-171, 174, 176. Rooney ML. 2000. Plastics in active packaging. In: Giles GA, Bain DR, editors. Materials and Development of Plastics Packaging for the Consumer Market. Boca Raton, FL: CRC Press. p. 105-129. Sadler GD, Braddock RJ. 1991. Absorption of citrus flavor volatiles by low density polyethylene. J Food Sci 56:35-37, 54.
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Sartore L, Penco M, Bignotti F, Peroni I, Gil MH, Ramos MA, D'Amore A. 2002. Grafting of selected presynthesized macromonomers onto various dispersions of silica particles. J Appl Polym Sci 85:1287-1296. SAS Institute. 1999. SAS user's guide: statistics, version 8.0. Cary, NC: SAS Institute. Shibamoto T. 1980. Flavor volatiles formed by heated milk. In: Charalambous G, editor. The Analysis and Control of Less Desirable Flavors in Foods and Beverages. New York: Academic Press. p. 241-265. Shimoda M, Ikegami T, Osajima Y. 1988. Sorption of flavor compounds in aqueous solution into polyethylene film. J Sci Food Agric 42:157-163. Shipe WF, Bassette R, Deane DD, Dunkley WL, Hammond EG, Harper WJ, Kleyn DH, Morgan ME, Nelson JH, Scanlan RA. 1978. Off-flavors of milk: Nomenclature, standards, and bibliography. J Dairy Sci 61:855-869. Staudinger J, Roberts PV. 2001. A critical compilation of Henry's law constant temperature dependance relations for organic compounds in dilute aqueous relations for organic compounds in dilute aqueous solutions. Chemosphere 44:561-576. Wood WE, Beaverson NJ, inventors; Cellresin Technologies, LLC, assignee. 2000 October 24. Rigid polymeric beverage bottles with improved resistance to permeant elution. U.S. patent 6,136,354. Zhou X, Mopper K. 1990. Apparent partition coefficients of 15 carbonyl compounds between air and seawater and between air and freshwater; implications for air-sea exchange. Environ Sci Technol 24:1864-1869.
148
CHAPTER 6 APPENDIX Table 5 - Solubility characteristics of molecular probes used in aqueous model solutions P0 b Mw kHcp a Max. Water Solubility (M/atm) (g/mol) (atm) (M) (mg/L) 1 Acetaldehyde 44.05 1.85E+01 1.15E+00 2.12E+01 9.34E+05 2 Propionaldehyde 58.08 1.82E+01 4.16E-01 7.57E+00 4.40E+05 3 Butyraldehyde 72.11 1.37E+01 1.47E-01 2.01E+00 1.45E+05 4 Valeraldehyde 86.13 9.21E+00 4.48E-02 4.13E-01 3.56E+04 5 Caproaldehyde 100.16 1.00E-01 1.42E-02 1.00E-01 1.00E+04 a Henrys law constant (Staudinger and Roberts 2001; Zhou and Mopper 1990). b Vapor pressure of pure molecular probe (Green and Maloney 1997). No. Molecular Probe
149
Table 6 - Odor and flavor thresholds of molecular probes in water and milka Odor Threshold in Water Flavor threshold in Water (ppm) (ppm) Acetaldehyde 1.20E-04 to 1.50E+01 1.50E-08 to 1.30E-05 Propionaldehyde 9.50E-03 1.70E-01 Butyraldehyde 9.00E-03 to 7.00E-03 7.00E-02 Valeraldehyde 1.20E-02 to 1.20E+00 7.00E-01 Caproaldehyde 5.00E-03 to 3.00E-02 1.60E-02 to 2.00E-01 a Odor and flavor thresholds obtained from literature (Fazzalari 1978). Molecular Probe Flavor Threshold in Milk (ppm) 1.30E+00 1.30E-01 5.00E-02
150
Figure 8 - TGA thermogram of nylon MXD6.
151
Figure 9 - TGA thermogram of D-sorbitol .
152
Figure 10 - TGA thermogram of -cyclodextrin.
153
Figure 11 - DSC thermogram of neat PET thermally pressed film.
154
Figure 12 - DSC thermogram of PET : nylon MXD6 thermally pressed film.
155
Figure 13 - DSC thermogram of PET : D-sorbitol thermally pressed film.
156
Figure 14 - DSC thermogram of PET : -cyclodextrin thermally pressed film.
157
Figure 15 - TGA thermogram of neat PET thermally pressed film. 158
Figure 16 - TGA thermogram of PET : nylon MXD6 thermally pressed film. 159
Figure 17 - TGA thermogram of PET : D-sorbitol thermally pressed film. 160
Figure 18 - TGA thermogram of PET : -cyclodextrin thermally pressed film. 161
Figure 19 TGA thermograms of neat PET and aldehyde scavenging PET films.
162
Figure 20 - HPLC chromatograms of (1) acetaldehyde, (2) propionaldehyde, (3) butyraldehyde, (4) valeraldehyde, and cyclodextrin blend for 1 day in aqueous solutions.
(5) caproaldehyde exposed to (A) Neat PET, (B) PET : nylon MXD6 blend, (C) PET : D-sorbitol blend, and (D) PET : -
163
Figure 21 - HPLC chromatograms of (1) acetaldehyde, (2) propionaldehyde, (3) butyraldehyde, (4) valeraldehyde, and cyclodextrin blend for 3 days in aqueous solutions.
164
165
166
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
140
a 122
120 100 80 60 40 20 0
a 117
b 89 c 70 d 58
Exposure Material
Figure 24 Total aldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 1 day of exposure.
a
167
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
140 120 100 80 60 40 20 0

a 117 b 99 c 77 d 60
e 48
Exposure Material
Figure 25 Total aldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 3 days of exposure.
a
168
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
140 120 100 80 60 40 20 0

a 114 b 91 c 70 d 56
d 45
Exposure Material
Figure 26 Total aldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 7 days of exposure.
a
169
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30
Molecular Probe Concentration ( M)
25
20
15
10
0
Acetaldehyde Propionaldehyde Butyraldehyde Valeraldehyde Caproaldehyde
Molecular Probe
Figure 27 Molecular probe concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 1 day of exposure.
170
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30
Molecular Probe Concentration ( M)
25
20
15
10
0
Molecular Probe
Figure 28 Molecular probe concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 3 days of exposure.
171
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
25 Molecular Probe Concentration ( M)
20
15
10
0
Molecular Probe
172
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30 Molecular Probe Concentration ( M)
25
20
15
10
0
Molecular Probe
173
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30
Acetaldehyde Concentration ( M)
25
20
15
10
0
Day 1 Day 3 Day 7 Day 14
Exposure Time
Figure 31 Acetaldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
174
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30
Propionaldehyde Concentration (M)
25
20
15
10
0
Exposure Time
Figure 32 Propionaldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
175
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30
Butyraldehyde Concentration (M)
25
20
15
10
0
Exposure Time
Figure 33 Butyraldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
176
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30
Valeraldehyde Concentration (M)
25
20
15
10
0
Exposure Time
Figure 34 Valeraldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
177
Neat PET
PET : Nylon MXD6
PET : D-Sorbitol
30
Caproaldehyde Concentration ( M)
25
20
15
10
0
Exposure Time
Figure 35 Caproaldehyde concentration in aqueous model solutions after exposure to neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
178
Acetaldehyde 25
Propionaldehyde
Butyraldehyde
Valeraldehyde
Caproaldehyde
20
15
10
0
PET PET : Nylon MXD6 PET : D-Sorbitol PET : Alpha Cyclodextrin
Exposure Material
Figure 36 Sorption of molecular probes per unit volume for neat PET and aldehyde scavenging PET blends after 1 day of exposure.
179
Acetaldehyde 25
Propionaldehyde
Butyraldehyde
Valeraldehyde
Caproaldehyde
20
15
10
0
PET PET : Nylon MXD6 PET : D-Sorbitol PET : Alpha Cyclodextrin
Exposure Material
Figure 37 Sorption of molecular probes per unit volume for neat PET and aldehyde scavenging PET blends after 3 days of exposure.
180
Acetaldehyde 30 25 20 15 10 5 0
PET
Propionaldehyde
Butyraldehyde
Valeraldehyde
Caproaldehyde
PET : Nylon MXD6
PET : D-Sorbitol
Exposure Material
Figure 38 Sorption of molecular probes per unit volume for neat PET and aldehyde scavenging PET blends after 7 days of exposure.
181
PET 25
PET : Nylon MXD6
PET : D-Sorbitol
Sorption (mg acetaldehyde / dm3 polymer)
20
15
10
0
Exposure Material
Figure 39 Sorption of acetaldehyde per unit volume for neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
182
PET 30
PET : Nylon MXD6
PET : D-Sorbitol
Sorption (mg propionaldehyde / dm3 polymer)
25 20 15 10 5 0
Exposure Material
Figure 40 Sorption of propionaldehyde per unit volume for neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
183
PET 25
PET : Nylon MXD6
PET : D-Sorbitol
Sorption (mg butyraldehyde / dm3 polymer)
20
15
10
0
Exposure Material
Figure 41 Sorption of butyraldehyde per unit volume for neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
184
PET 25
PET : Nylon MXD6
PET : D-Sorbitol
Sorption (mg valeraldehyde / dm3 polymer)
20
15
10
0
Exposure Material
Figure 42 Sorption of valeraldehyde per unit volume for neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
185
PET 18
PET : Nylon MXD6
PET : D-Sorbitol
Sorption (mg caproaldehyde / dm3 polymer)
16 14 12 10 8 6 4 2 0
Exposure Material
Figure 43 Sorption of caproaldehyde per unit volume for neat PET and aldehyde scavenging PET blends after 1, 3, 7, and 14 days of exposure.
186
Prediction of Sorption in a Beverage Container Materials and Methods The surface area of beverage containers was determined using a prototype surface analyzer (CS Technologies, OmniSurface Machine Vision System, American Fork, UT). This analyzer projects light onto the object that is being analyzed and casts a shadow of the object on a shadow box. The object is rotated on a manual turntable connected to a computer workstation. A digital camera, connected to the computer workstation, takes a digital image of the objects shadow at 8 increments when the turntable is rotated. The computer workstation then calculates the surface area of the object based on the area of 45 two-dimensional images. Translucent and transparent packaging materials required the application of thin epoxy paint in order to prevent transmission of light. Surface area measurements for beverage containers showed excellent precision demonstrated by small standard deviations among containers tested. Results and Discussion The amount (mg) of molecular probes sorbed per unit volume (dm3) for test films after one, three, seven, and fourteen days were calculated and are presented in Figures 1-4. Previous trends discussed for sorption amounts and rates by test films are also seen in this presentation format. However, sorption amounts calculated on a per volume or surface area basis for packaging material allows one to determine the theoretical concentration of molecular probes that can be removed from a container. The volume of packaging material found in a container can easily be calculated after accurately weighing the empty container and determining the density of the packaging material. Alternatively, one can measure the surface area of a beverage container in order to predict scalping capacity. The surface area of simply shaped containers such as cylinders and cubes can be calculated using geometric equations, however, most beverage containers will require more sophisticated equipment for surface area measurement. The sorption capacity of molecular probes by several beverage containers in different sizes and geometric shapes was predicted from data obtained for sorption amount after fourteen days of exposure (Figures 44-50). Predictions assume containers were manufactured from neat PET and blended PET materials. Storage conditions and composition of the aqueous model solution are also assumed.
187
The sorption capacity for molecular probes by larger containers is greater then smaller containers due to their increased overall surface area. For instance, predicted sorption amounts for acetaldehyde by 8 fl. oz. and 1 gallon containers consisting of PET : -cyclodextrin material are 345 and 2,171 g. However, the concentration of molecular probe removed by the container is related to its surface area to volume ratio. An 8 fl. oz. container which has a surface area to volume ratio of 1.12 cm2 / mL consisting of PET : -cyclodextrin material can remove 1,463 ppb of acetaldehyde. A 1 gallon container comprised of the same material with a surface area to volume ratio of 0.44 cm2 / mL is only predicted to remove 574 ppb of acetaldehyde from solution.
188
Figure 44 - Surface area measurementsa and theoretical scalping abilityb of 8 fl. oz. beverage container. Brand 8th Continent Product Soy milk Low fat Vanilla Size (fl. oz.) 8 Size (mL) 236 Packaging material HDPE (white) Surface area (cm2) 263 7 Surface area (cm2) : Volume (mL)ratio 1.12 a Surface area measurements performed using OmniSurface Machine Vision System.
PET PET:Nyl. MXD6 PET:D-Sorbitol PET:-Cdex. (g) (ppb) (g) (ppb) (g) (ppb) (g) (ppb) Acetaldehyde 53 224 196 830 316 1337 345 1463 Propionaldehyde 41 175 167 707 241 1020 326 1381 Butyraldehyde 76 324 157 667 188 799 229 972 Valeraldehyde 101 429 134 569 150 637 182 772 Caproaldehyde 84 356 78 332 96 407 122 517 b Calculated absorption of molecular probes assumes the following conditions: 1) PET packaging material, 2) ambient storage temperature, 3) exposure time of fourteen days.
Molecular probe
189
Figure 45 - Surface area measurementsa and theoretical scalping abilityb of 12 fl. oz. beverage container. Brand Land O Lakes Line description Grip n Go Product 2% Reduced fat milk Size (fl. oz.) 12 Size (mL) 355 Packaging material HDPE (white) Surface area (cm2) 344 1 Surface area (cm2) : Volume (mL)ratio 0.97 a Surface area measurements performed using OmniSurface Machine Vision System.
Molecular probe
190
Figure 46 Surface area measurementsa and theoretical scalping abilityb of 14 fl. oz. beverage container. Brand Hershey Product Chocolate milk Fat free Calcium fortified Size (fl. oz.) 14 Size (mL) 414 Packaging material HDPE (white) Surface area (cm2) 377 6 2 Surface area (cm ) : Volume (mL)ratio 0.91 a Surface area measurements performed using OmniSurface Machine Vision System.
Molecular probe
191
Figure 47 - Surface area measurementsa and theoretical scalping abilityb of 16 fl. oz. beverage container. Brand Nestle Line description Nesquik Product Chocolate milk Size (fl. oz.) 16 Size (mL) 473 Packaging material PET (clear) Surface area (cm2) 410 1 Surface area (cm2) : Volume (mL)ratio 0.87 a Surface area measurements performed using OmniSurface Machine Vision System.
Molecular probe
192
Figure 48 - Surface area measurementsa and theoretical scalping abilityb of 32 fl. oz. beverage container. Brand Kroger Product Grade A Skim milk Size (fl. oz.) 32 Size (mL) 946 Packaging material HDPE (white) Surface area (cm2) 640 6 2 Surface area (cm ) : Volume (mL)ratio 0.68 a Surface area measurements performed using OmniSurface Machine Vision System.
Molecular probe
193
Figure 49 - Surface area measurementsa and theoretical scalping abilityb of 0.5 gal. beverage container. Brand Valley Rich Product 2% Reduced fat milk Size (U.S. gal.) 0.5 Size (mL) 1890 Packaging material HDPE (opaque) Surface area (cm2) 1115 10 2 Surface area (cm ) : Volume (mL)ratio 0.59 a Surface area measurements performed using OmniSurface Machine Vision System.
PET PET:Nyl. MXD6 PET:D-Sorbitol PET:-Cdex. (g) (ppb) (g) (ppb) (g) (ppb) (g) (ppb) Acetaldehyde 224 119 830 439 1338 708 1464 774 Propionaldehyde 175 92 708 374 1021 540 1382 731 Butyraldehyde 324 171 668 353 799 423 972 514 8Valeraldehyde 430 227 569 301 637 337 772 409 Caproaldehyde 356 188 332 176 407 216 517 274 b Calculated absorption of molecular probes assumes the following conditions: 1) PET packaging material, 2) ambient storage temperature, 3) exposure time of fourteen days.
Molecular probe
194
Figure 50 - Surface area measurementsa and theoretical scalping abilityb of 1 gal. beverage container. Brand Valley Rich Product 2% Reduced fat milk Size (fl. oz.) 1.0 Size (mL) 3780 Packaging material HDPE (opaque) Surface area (cm2) 1654 6 2 Surface area (cm ) : Volume (mL)ratio 0.44 a Surface area measurements performed using OmniSurface Machine Vision System.
Molecular probe
195

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SECTION III SORPTION BEHAVIOR OF SELECTED ALDEHDYE SCAVENGING AGENTS IN POLY(ETHYLENE TEREPHTHALATE) BLENDS

Formatted in Accordance with the Journal of Food Science Style Guide.

Aqueous Model Solution

PET : Nylon MXD6

140 120 100 80 60 40 20 0

Total Aldehyde Concentration ( M)

PET : Nylon MXD6

PET : Alpha Cyclodextrin

PET : Nylon MXD6

PET : Alpha Cyclodextrin

PET : Nylon MXD6

PET : Alpha Cyclodextrin

PET : Nylon MXD6

PET : Alpha Cyclodextrin

PET : Nylon MXD6

PET : Alpha Cyclodextrin

Sorption (mg probe / dm3 polymer)

PET : Nylon MXD6

PET : Alpha Cyclodextrin

Caproaldehyde (K) 382 367 465 587

Figure 8 - TGA thermogram of nylon MXD6.

Figure 9 - TGA thermogram of D-sorbitol .

Figure 10 - TGA thermogram of -cyclodextrin.

Figure 11 - DSC thermogram of neat PET thermally pressed film.

Figure 12 - DSC thermogram of PET : nylon MXD6 thermally pressed film.

Figure 13 - DSC thermogram of PET : D-sorbitol thermally pressed film.

Figure 14 - DSC thermogram of PET : -cyclodextrin thermally pressed film.

Figure 15 - TGA thermogram of neat PET thermally pressed film. 158

Figure 17 - TGA thermogram of PET : D-sorbitol thermally pressed film. 160

Figure 18 - TGA thermogram of PET : -cyclodextrin thermally pressed film. 161

Aqueous Model Solution

PET : Nylon MXD6

Total Aldehyde Concentration ( M)

Aqueous Model Solution

PET : Nylon MXD6

140 120 100 80 60 40 20 0

Total Aldehyde Concentration ( M)

Aqueous Model Solution

PET : Nylon MXD6

140 120 100 80 60 40 20 0

Total Aldehyde Concentration ( M)

Aqueous Model Solution

PET : Nylon MXD6

Molecular Probe Concentration ( M)

Aqueous Model Solution

PET : Nylon MXD6

Molecular Probe Concentration ( M)

Aqueous Model Solution

PET : Nylon MXD6

25 Molecular Probe Concentration ( M)

Aqueous Model Solution

PET : Nylon MXD6

30 Molecular Probe Concentration ( M)

Aqueous Model Solution

PET : Nylon MXD6

PET : Alpha Cyclodextrin

Aqueous Model Solution

PET : Nylon MXD6

PET : Alpha Cyclodextrin

Propionaldehyde Concentration (M)

Aqueous Model Solution

PET : Nylon MXD6

PET : Alpha Cyclodextrin

Butyraldehyde Concentration (M)