Polymer Testing 30 (2011) 463471

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material Properties

Release of butylated hydroxytoluene (BHT) from Poly(lactic acid) lms

Heberto Ortiz-Vazquez a, Joongmin Shin b, Herlinda Soto-Valdez a, Rafael Auras c, *
a b c

Centro de Investigacin en Alimentacin y Desarrollo, A.C., CTAOV, Apdo. Postal 1735, Hermosillo, Sonora 83304, Mexico Engineering and Technology Department, University of Wisconsin-Stout, Menomonie, WI 54751, USA School of Packaging, Michigan State University, East Lansing, MI 48824-1223, USA

a r t i c l e i n f o
Article history: Received 29 January 2011 Accepted 9 March 2011 Keywords: Diffusion Partition coefcient PLA Solubility

a b s t r a c t
The addition of butylated hydroxytoluene (BHT) to poly(lactic acid), PLA, lms and its release into to three simulants (water, 95% ethanol and coconut oil) were evaluated. The decomposition temperature and tensile strength decreased in PLA-BHT lms. The diffusion kinetics of BHT into ethanol 95% at 23, 31 and 43  C gave diffusion coefcients between 1011 and 10 9 cm2 s1. The activation energy was calculated as 164.7 27.7 kJ mol1 for the diffusion of BHT from PLA-BHT lms in ethanol. Release of BHT in water at 13, 23 and 43  C and 100 days was not detected at the level of quantication of 1 mg of BHT.mL1 of solution. PLA and PLABHT lms stored in water at 43  C for 100 days showed a reduction of 44% in the Mn. Films stored in fractionated coconut oil released 3.9 and 13.2% of BHT at 23 and 43  C, respectively after 100 days. 2011 Elsevier Ltd. All rights reserved.

1. Introduction Poly(lactic acid) (PLA) is a linear aliphatic polyester synthesized from lactic acid monomer by catalytic ringopening polymerization of lactide. PLA can be produced from renewable sources, and it is biodegradable and compostable [1,2]. The ester linkages in the polymer (Fig. 1a) are sensitive to both enzymatic and chemical hydrolysis, presenting a challenge to stability during storage but important in promoting biodegradation after disposal [3,4]. PLA degradation behavior and rate depend on its molecular structure and morphology as well as media-related factors [18]. The physical properties of PLA lms can be tailored by changing the composition and processing conditions [1,5]. Applications for PLA have focused on packaging as well as medical and pharmaceutical systems [1,2,5,6]. PLA is approved by the U.S. Food and Drug Administration (FDA) for use in food-contact materials [911]. PLA microspheres have been widely used in medical applications [12]. Studies on the loading and release of various chemical compounds

* Corresponding author. Tel.: 1 517 432 3254; fax: 1 517 353 8999. E-mail address: aurasraf@msu.edu (R. Auras). 0142-9418/$ see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymertesting.2011.03.006

from PLA include bioactives such as resveratrol [13], antioxidants such as a-tocopherol [14], drugs such as methotrexate [15], and recombinant human bone morphogenic protein [1618] have been conducted. An interesting area of development for PLA lms is the release of active compounds such as antimicrobials and antioxidants [13,14,19]. Butylated hydroxytoluene (BHT), or 2,6-bis(1,1-dimethylethyl)-4-methylphenol (Fig. 1b), is a lipid-soluble antioxidant commonly used in the plastics, pharmaceutical and food industries. BHT terminates free-radical chain reactions by donating hydrogen atoms to free radicals producing more stable compounds. In the U.S., direct addition of BHT to some food emulsion is specically regulated, but BHT is generally recognized as safe for use in food when the total content of antioxidants is not over 0.02% of the fat or oil content [20,21]. An alternative mechanism for adding antioxidants is to use a loaded functional membrane in contact with the food product to maintain a constant concentration of the additive in the product during storage [22]. Addition of antioxidants to polyolens is a common practice during lm manufacture to protect the polymer from degradation. BHT is used at concentrations up to 500 kg1 in polyolens for this purpose [23]. During lm

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Fig. 1. Structure of (a) PLA and (b) BHT.

processing, some of this antioxidant is lost (degrades and/ or decomposes) because of its ability to function as a freeradical scavenger, and is lost to the environment because of high volatility at processing temperatures [24]. Therefore, to provide shelf life extension for oxidation-susceptible products, functional membranes loaded with BHT must be formulated with higher antioxidant concentrations than typically used in polyolen lms. Studies of the release kinetics of BHT from polyolen lms have demonstrated an appropriate rate of release and a high mobility of BHT towards fatty foods and to the environment [2527]. However, no comparable research has been conducted with PLA. The present study was designed to evaluate the effects of BHT addition on the physical, optical, thermal, mechanical and barrier properties of PLA lms, and further evaluate the release kinetics of BHT to different simulants: ethanol, water and oil. 2. Experimental part 2.1. Materials Poly(94% L-lactic acid) resin was procured from NatureWorks (Blair, NE, USA). BHT, 99% purity, was purchased from TCI America (Tokyo, Japan). Tetrahydrofurane (THF), methanol, and water (all high performance liquid chromatography (HPLC) grade) were obtained from Sigma Aldrich (St. Louis, MO, USA). Ethanol (95%) was purchased from Aaper Alcohol and Chemicals Co. (Shelbyville, KY, USA). Fractionated coconut oil was obtained from Oils by Nature Inc. (Solon, OH, USA). 2.2. PLA lm production PLA lms without BHT (PLA, control) and with 0.015 g BHT per g of PLA resin (PLA-BHT) were extruded in a pilotplant scale blow-extrusion machine (Beutelespacher, Mexico). Extrusion temperatures were 165  C for the feed zone and 170  C for all the subsequent zones to the die zone. A homogeneous distribution of BHT in the PLA lms was obtained by pelletizing the extruded PLA-BHT mix and discarding the heads and tails of each extruded batch. The average thickness of all lms was 50.8 8.5 mm. 2.3. Quantication of BHT in PLA-BHT lms The amount of BHT in the extruded lms was quantied by HPLC. To extract BHT, sample sections of 0.042 0.001 g of the PLA-BHT lms were manually homogenized in 10 mL

of methanol and placed in an ultrasound bath (Ultrasonic Cleaner, ColeParmer, Vernon Hills, IL, USA) for 3 h. The HPLC system used was a Waters Alliance 2695 (Waters, Milford, MA, USA) equipped with an auto sampler and coupled to a dual absorbance detector (Waters 2487) at 277 nm wavelength. A C18 Nova-Pak column (3.9 150 mm; Waters) protected with a C18 guard column was employed. After the 3-h extraction, 10-mL aliquots of the BHT solution were injected, with a run time of 5 min per injection, and isocratically eluted with 90% methanol and 10% water. To check that all the BHT was extracted, each sample solution was placed in the ultrasonic bath for an additional 1 h and HPLC analysis was repeated. All samples were tested in triplicate. Standard solutions of BHT in methanol at concentrations from 1 to 31 mg mL1 were used to produce a calibration curve for the quantication of the analyte (R2 0.9992). BHT retention time was 1.2 min, and the limit of quantication (LOQ) was 1 mg mL1. Recovery rates were 97.68 1.31%. 2.4. Evaluation of BHT release from PLA lms into simulants BHT diffusion from PLA and PLA-BHT lms into 95% ethanol, water and fatty food simulants was carried out in accordance with ASTM D4754-98, using a 40-mL glass amber vial with a screw hole cup and a sealing PTFE/silicon septum as the migration test cell. Circular sections (2.0 cm in diameter) were cut from the lms. Fourteen circled lm sample placed in the test cell were separated by means of a glass bead. Four or ve cell replicates of PLA and PLA-BHT lms were held at each storage temperature for specic times as indicated for each simulant below. 95% Ethanol: Cells were lled with 30 mL of 95% ethanol and stored at 23, 31 and 43  C (0.5  C) for 460, 360 and 152 h, respectively. Samples of ethanol (1 mL) were collected periodically during storage and 10-mL aliquots were injected directly into the HPLC; the remaining samples were returned to their respective vials after analysis to avoid changing the simulant volume. BHT quantication in ethanol was performed as described in the previous section. The calibration curve for BHT in ethanol was prepared from standard solutions containing 2.0 200 mg mL1 of BHT; the LOQ was 1.0 mg mL1. Water: Cells were lled with 35 mL of water and stored at 13, 23 and 43  C (0.5  C) for 100 days. Periodic sampling was carried at 5-day intervals for cells at 43  C, at 10-day intervals for cells at 23  C, and at 15-day intervals for cells at 13  C. BHT quantication in water was performed with the same method and calibration curve described in the previous section for ethanol. Coconut oil: Cells were lled with 35 mL of coconut oil and stored at 13, 23 and 43  C (0.5  C) for 100 days. Periodic sampling was carried out as described above for water. BHT quantication in coconut oil was performed by the same HPLC system mentioned above, but with a different methodology. A 10-mL sample volume was injected, with a run time of 18 min per injection. Elution was as follows: 90% methanol and 10% water at 1 mL min1 ow and a gradient program of 2.5 min; then gradient elution from 90:10 to 100:0 (methanol/water) and ow reduction to 0.75 mL min1, maintained for 1.3 min. Finally,

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a 1 min gradient elution from 100:0 to 90:10 and ow increase to 1 mL min1, maintained for 13.2 min. The calibration curve was prepared with concentrations of BHT from 1 to 4 mg mL1 in fractionated coconut oil with 0.1wt.% ter-butylhydroquinone (TBHQ). The LOQ was 1.0 mg mL1. 2.5. BHT release models An analytical solution for the one-dimensional diffusion of BHT from a slab and in a limited volume solution was used to determine the diffusion coefcient (D) according to Ficks second law [30]:
N o n X M1 2a1 a 2 1 exp Dq2 t t =l 2 2 MN 1 a a qn n1

and T is the temperature in K. Ea was obtained from the slope of tting a linear equation to a plot of the reciprocal of temperature (1/T) vs. the natural logarithm of D (Ea -slope$R) [34,36]. 3. Molecular weight determination Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution or polydispersity index (PDI) of the PLA and PLA-BHT lms, before and after exposure to simulants, were determined by dissolving the samples in THF at a concentration of 20 mg of lm per 10 cc of THF. A 100-mL aliquot of each sample solution was injected into a gel permeation chromatograph (GPC) equipped with the following components: a Waters 1515 isocratic pump, a Waters 717 autosampler, a series of three columns (HR2, HR3, and HR4) and a Waters 2414 refractive index detector interfaced with Waters Breeze software, all from Waters, Inc. A ow rate of 1 mL min1, a run time of 45 min and a temperature of 35  C were used. A polystyrene standard kit in the range of 1.31 103 to 3.64 106 Da was used as an external standard to create a calibration curve for molecular weight determination. Analyses were carried out in triplicate. 4. Optical properties characterization UVvisible spectroscopy was used to determine the light transmission of the PLA and PLA-BHT lms before and after exposure to simulants. UV analysis was performed using a PerkinElmer Lambda 25 (Waltham, MA, USA) with an integrating reectance spectroscopy accessory (model RSA-E20, Labsphere, North Sulton, NH, USA) with measurements carried out at 480 nm min1 and a wavelength range of 190800 nm in transmittance (%) mode. All results are presented as transmittance values. At least ve samples were scanned. Tristimulus color values of lms were obtained with a LabScan XE (HunterLab, Reston, VA, USA) and converted by the instrument to the Hunter L*, a*, b* values. For each lm type, ve samples were measured and values averaged. The E value, which indicates the total color difference, takes into account the differences between the L*, a* and b* values of the sample and control; E was calculated as expressed in Equation (6):

(1)

where the qn are the non-zero positive roots of tan qn -aqn, and a is expressed as:

VS VP $KP;S

(2)

where VS and VP are the molar volume of the simulant and the polymer, respectively; KP,S is the partition coefcient of BHT between PLA and the simulant, which can be assumed in contact for low concentrations and calculated from the ratio of the concentration of BHT in PLA (CP,N) and the simulant (CS,N) at equilibrium according to the following equation:

KP;S

CP;N CS;N

(3)

If the amount of solvent can be considered innite (i.e.,

a>>1 since VS>>VP and/or KP,S<1), Equation (1) can be

simplied as:

) ( 2 N Mt 8 X 1 D2m 1 p2 t 1 2 exp p m 0 2m 12 l2 MN

(4)

To t the data to Equation (1), the ratio of the BHT concentration in solution at time t to the BHT concentration in solution at equilibrium (Mt/MN) was plotted against the square root of time, and the diffusion coefcients (D,cm2$s1) were calculated for each temperature. In Equations (1) and (4), l is the thickness of the lm in cm. The value of D was determined by minimizing the sum of the squares errors (SSE) of the measured and estimated values. To determine the t of the experimental data to Equations (1) and (4), the non-linear regression (nlint) function in MATLAB R2010b (MathWorks, Natick, MA, USA) was applied to the data [3135]. To determine the effect of temperature on the diffusion of BHT from the PLA lms, the activation energy (Ea) was calculated using the Arrhenius equation for diffusion:

DE

p DL2 Da2 Db2

(6)

where DL LPLABHT-LPLA, Db bPLABHT-bPLA.

Da aPLABHT-aPLA, and

5. Thermal properties characterization The glass transition temperature (Tg), melting temperature (Tm) and the percent crystallinity (Xc) of the PLA and PLA-BHT lms were determined using a differential scanning calorimeter (DSC Q-100; TA Instruments, New Castle, DE, USA). Transition temperatures were obtained in accordance with ASTM D3418-03. Percent crystallinity was determined in accordance with ASTM D3417-99 and Equation (7):

 D D0 exp

Ea RT

 (5)

where D is the diffusion coefcient, Do is the pre-exponential factor of diffusion, Ea is the activation energy of diffusion, R is the ideal gas constant (8.3145 J K1 mol1)

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DHm DHc cc wt :% 100$ o DHm 1 x

(7)

9. Results and discussion From the initial 1.5 wt.-% BHT added to the PLA resin, only 0.79 0.05 wt.-% of BHT was present in the extruded PLABHT lms. The loss of 52% of the added BHT during extrusion could be attributed to several factors: poor mixing of the single extrude, BHT evaporation, thermal degradation and the antioxidant activity of BHT [35]. BHT has a lower melting point (7073  C) than PLA, lower ash point (w127  C), high volatility with a TD of around 157  C, and a high vapor pressure (70 mmHg at 200  C) [24,36]. PLA-BHT lms were extruded at temperatures around 165  C, which would contribute to the high loss of BHT. Similar losses of BHT in polyolens were previously reported [24,3439]. Physical, optical, thermal, mechanical and barrier properties of the PLA and PLA-BHT lms are shown in Table 1. The addition of BHT did not signicantly affect the molecular weight properties of the PLA lm; the lower Mw and Mn of both lms compared to the PLA resin indicated the loss of residual water during PLA resin processing [1,5]. Compared to the control PLA lm, the PLA-BHT lm had slightly lower L* and higher a* values, indicating a slightly darker and more reddish-yellow lm, which could be attributed to lower light transmission between 675 and 678 nm where the red light region is located. Under thermooxidative conditions, BHT forms colored by-products such as quinone methide and stilbene bis(quinone) (3,30 ,5,50 -

where DHm is the enthalpy of fusion, DHc is the enthalpy of cold crystallization, DHm is the heat of melting of purely crystalline PLA (93.7 J g1) [1] and x is the amount of BHT in the sample. Values for Tg, Tm and cc were determined from the rst heating cycle from room temperature to 180  C at 10  C min1. The decomposition temperature (TD) and the temperatures where the samples lost 5, 50 and 95% of the weight (i.e., T5%,T50%,T95%) were obtained in accordance with ASTM E1131-03 using a TGA TA 2950 thermogravimetric analyzer (TA Instruments). The specimens were heated at the rate of 10  C min1 within a range of 30 up to 800  C in the presence of N2 and above 90psi. All tests were done in triplicate and data were analyzed with Universal Analysis Software (Version 3.9A). 6. Mechanical properties characterization Tensile strength, tensile strength at break, and elongation at break of the PLA and PLA-BHT lms were measured with an Instron 5565 Universal Testing machine (Instron, Canton, MA, USA) according to ASTM D882-02. Tests were performed on ve samples of each material at 23  C with an initial grip separation of 101.6 mm and a crosshead speed rate of 58.8 mm min1. 7. Barrier properties characterization The water vapor transmission rate (WVTR) of the lms was measured with a PermatranTM C3/31 (Modern Controls Inc., Minneapolis, MN, USA) according to ASTM F1249 at 37.8  C with 100% RH. WVTR values were used to calculate the water vapor permeability (WVP) from Equation (8):

Table 1 Optical, physical, thermal, mechanical, and barrier properties of the PLA and PLA-BHT extruded lms. Property Molecular Weighta PLA PLABHT 135.7 88.2 1.72 92.15 1.01 0.68 0.35 57.2 150.3 0.4 0.5 360.3 401.8 420.6 407.6 54.0 1.6A 6.8A 0.07A 0.05B 0.01B 0.04A 0.06 0.2A 0.1A 0.1A 0.2A 1.4B 0.4A 1.2A 0.5B 2.5B

WVP

WVTRkg thicknessm partial pressurePa times aream2

(8)

The oxygen transmission rate (OTR) was measured with an Illinois 8001 system (Illinois Instruments Inc., Johnsburg, IL, USA) according to ASTM D3985 at 23  C and 100% RH. OTR values were used to calculate the oxygen permeability (OP) from Equation (9). All lm measurements were performed in triplicate.

OTR kg thicknessm OP partial pressurePa times aream2

(9)

Mw, kDa 151.8 1.59A Mn 90.6 2.3A PDI 1.67 0.03A Optical L 92.48 0.07A a* 1.08 0.01A b* 0.70 0.02A DE n/a Tg,  C 57.8 0.1A Thermalb T m,  C 151.6 0.1A Hm, J g1 0.3 0.1A Xc, % 0.3 0.1A T5%, C 366.7 1.3A T50%, C 403.1 0.3A T95%,  C 422.3 1.1A TD,  C 408.7 0.0A Mechanical Tensile 59.3 2.2A strength, MPa Tensile strength 48.2 4.6A at break, MPa Elongation at 5.8 1.6A break, % Barrier OP 1018, 2.3 0.5A kg.m.m2.s1.Pa1 WVP 1015, 1.4 0.1A kg.m.m2.s1.Pa1

44.7 2.8A 4.1 1.0A 2.1 0.2A 1.2 0.2A

8. Statistical analysis Students t-test, Tukeys HSD, TukeyKramer and oneway ANOVA tests were performed to conduct multiple comparisons of the experimental data set for PLA and PLABHT lms at a 0.05 using JMP 8.02 software (SAS Institute Inc., NC, USA).

Values are given as means SD (n 5 for molecular weight, optical, and mechanical properties; n 3 for thermal and barrier properties). Values with different superscript letters are signicantly different at type I error (a) of 0.05, using the TukeyKramer test. n/a:Not applicable. a Properties of PLA resin: Mw 150.6 9.9 kDa; Mn 85.6 2.5; and PDI 1.76 0.4. b T5%, T50% and T95% are temperatures at which samples lost 5, 50 and 95% of weight, respectively.

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Fig. 2. UV and visible light transmission (%) of PLA and PLA-BHT lms.

tetra-bis(tert-benzoquinone), which could be responsible for this small color change of the PLA-BHT lms [24]. Fig. 2 shows the light transmission rate of the PLA and PLA-BHT lms. The benzene ring in BHT (Fig. 1b) absorbs in the UVlight region at 280 nm maximum wavelength [40]. No signicant differences were detected in Tg, Tm and Xc between the PLA and PLA-BHT lms. However, the addition of BHT to PLA resulted in reduced T5% and TD attributed mainly to the presence of degradation products during extrusion (Fig. 3). Yuzay et al. [41] found that the addition of synthetic zeolite to PLA also reduced TD. The tensile strength decreased signicantly due to the addition of BHT. The barrier properties of both PLA and PLA-BHT lms were not signicantly different; similar OP and WPC of 1.39 0.14 1018 and 1.48 0.07 1014 kg m m2 s1 Pa1, respectively, were reported previously [6,42]. Variation of 1020% in OP and WVP coefcients are

easily attributed to PLA processing and changes in lm structure characteristics [43]. Fig. 4 shows the diffusion of BHT from the PLA-BHT lm into 95% ethanol over time at the three temperatures studied. Equilibration time decreased with an increase in temperature: at 23, 31 and 43  C, equilibrium was obtained after 364, 96 and 2.5 h, respectively. At the end of the experiment, 91, 84 and 65% of the BHT from the PLA-BHT lm was released into solution at 43, 31 and 23  C, respectively. Diffusion coefcients were estimated from Fig. 4 according to Equation (1) or (4), and values are shown in Table 2. Han et al. [38] evaluated BHT diffusion from HDPE/LDPE lms into 100% ethanol and reported D values of 2.20 1010, 8.65 1011 and 2.34 1011 cm2 s1 at 40, 31 and 23  C, respectively. In spite of the differences between polyolen and PLA polymers, the reported D values at 23 and 31  C are similar to those found in the present study. Value at 40  C is one order of magnitude lower than that determined for PLA at 43  C since temperature near the Tg can accelerate diffusion. Using the data obtained in the present study, a plot of ln(D) vs. 1/T (not shown) produced a straight line (R2 0.973) with an Ea of 164.7 27.7 kJ mol1. The activation energy obtained is similar to that of other polymers with hydrocarbon chains (polyolens) [27]. Reynier et al. [39] reported that Ea of the diffusion of a series of additives from polypropylene ranged between 100 and 250 kJ mol1. No release of BHT from the PLA-BHT lm in water was detected at the LOQ of 1 mg mL1 at 13, 23 or 43  C for at least 100 days (not shown). This result can be explained by the lack of afnity and solubility of BHT in water. BHT, PLA and water are polar compounds. Regular solution theory (RST) can be used to predict the interaction between PLA, BHT and the different simulants. The known dispersion (dD), polar (dP) and hydrogen bonding (dH) solubility parameters of BHT, PLA, ethanol, water and coconut oil are

Fig. 3. Weight change (%) as a function of temperature in  C for PLA and PLA-BHT lms.

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Table 3 Dispersion (dD), polar (dP), and hydrogen bonding (dH) parameters for PLA, BHT and various simulants. Material

dD
MPa1/2

dP
MPa1/2 5.9 2.6 4.3 2 16

dH
MPa1/2 6.4 6.6 9.5 2 42.3

Dd from PLAa
MPa1/2 0 2.37 20.5 6.7 26.1

Dd from BHTa
MPa1/2 2.37 0 17.9 5.7 25.8

Ref.

PLA BHT Ethanol Coconut oil Water

17.6 16.5 7.73 16 15.5

[1] [47] [47] [47] [47]

a Relative distance, Dd, was calculated according to Dd2 4(dDpdDs)2 (dPp-dPs)2 (dHp-dHs)2, where the second subscript p indicates PLA

or BHT and the second subscript s indicates the simulant.

indicated in Table 3. According to RST, the absolute distance between the dD, dP and dH can be used to estimate the afnity between compounds [4447]. Thus, the greater the distance between BHT, ethanol, water, coconut oil and PLA, the lower the afnity between these compounds. Table 3 shows a calculated relative distance (Dd) of 2.37 MPa1/2 between PLA and BHT, 20.5 MPa1/2 between PLA and ethanol, 6.7 MPa1/2 between PLA and coconut oil, and 26.1 MPa1/2 between PLA and water, indicating a higher afnity between PLA and BHT than between PLA and the solvents. As denoted by the higher afnity between PLA and BHT and the lower afnity between BHT and water, no release of BHT in water is expected and BHT was not detected. Fig. 5 shows the release of BHT from PLA-BHT lms in coconut oil over time at 13, 23 and 43  C. The concentration of BHT detected in coconut oil at 13  C remained below the LOQ (1 mg mL1) over 100 days. The highest BHT concentrations were detected at day 90 at 23  C (1.11 mg mL1) and at day 100 at 43  C (3.78 mg mL1), which corresponded to release of 3.91 and 13.2% of BHT at 23 and 43  C, respectively. These values are considerably lower than the results obtained for the PLA-BHT lm in 95% ethanol (65 and 99% of BHT release at 23 and 43  C, respectively). Limm and Hollield [34] reported D values of 2.70 1010 and 6.39 109 cm2 s1 at 30 and 60  C, respectively, for BHT

Table 2 Diffusion coefcients (D) of BHT from PLA-BHT lm into 95% ethanol at various temperatures. Film thickness was 50.8 8.5 mm (2.00 0.33 mil). Temperature Kp,s


D 1010a cm s
2. 1

RMSEb

23 31 43

61.14 2.1961 0.295 0.027A (0.2400.349) 1.14E-05 20.54 6.5384 0.895 0.079B (0.7361.053) 1.40E-05 12.61 10.6506 19.04 0.67C (17.8120.26) 8.32E-06

a Values are expressed as best t values for four replications standard error and 95% asymptotic condence intervals. At 23 and 31 C, D was estimated according to Equation (1); at 43  C, equilibrium was obtained at 2.5 h so D was estimated according to Equation (4) which provided a best t with smaller RMSE. Values with different superscript capital letters are signicantly different at type I error (a) of 0.05. b RMSE, root mean square error.

Fig. 5. Release of BHT from PLA-BHT lms in coconut oil at 13, 23 and 43  C over 100 days.

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Fig. 6. Weight average molecular weight, Mw, for PLA resin as well as PLA and PLA-BHT lms before and after exposure to stimulants at 13, 23 and 43  C: in water and coconut oil for 100 days and in 95% ethanol for 16 days. * indicates that the Mw is signicantly different at type I error (a) of 0.05 with respect to the corresponding lm before storage; the short red dotted line indicates the initial Mw for PLA and PLA-BHT lms.

release from HDPE in corn oil. Soto-Cant et al. [27] reported a D value of 6.2 1012 cm2 s1 for BHT in a LDPE layer of a co-extruded lm (polyamide 6/66-LDPE) in contact with cheese (24% fat) at 5  C. The low D value obtained was attributed to the low storage temperature, relatively low level of fat and physical state (semisolid) of the cheese. Fig. 5 indicates that BHT release at 43  C does not follow Ficks law of diffusion; therefore, the diffusion coefcient could not be directly determined by Equation (1) and/or (4). If for estimation purposes we assumed Fickian behavior based on the maximum release of BHT of 3.78 mg mL1 in coconut oil at 43  C, D values between 1014 and 1016 cm2 s1 for releasing BHT from the PLABHT lm in coconut oil were estimated using HSPiP prediction tools [47]. Although more BHT was released from the PLA-BHT lm into oil than into water, the total quantities released in both simulants are still very low. UV light transmission in the 280 nm wavelength range did not signicantly change for the samples stored in coconut oil and water at 13 and 23  C for 100 days. However, in the samples stored in water at 43  C, a reduction of the transmission from 94 to 29% between 290 and 800 nm was observed (Figure not shown). Samples stored at 43  C show a color change with respect to the initial samples of DE 3.186 due to a positive change in the L parameter, indicated by a loss of transparency in the lms. PLA polymers are very sensitive to hydrolysis; therefore chain scission and chain breaking could be taking place at temperatures near Tg. Fig. 6 shows the average molecular weight reduction of the PLA and PLA-BHT lms before and after exposure to water, coconut oil and 95% ethanol. Reductions in Mw were found in the PLA and PLA-BHT lms exposed to 43  C in water and ethanol. The PLA and PLABHT lms are both amorphous, so the degradation rate followed a core-accelerated bulk erosion process removing water soluble oligomers and monomers [8]. The reduction in Mn of amorphous PLA and PLA-BHT lms in water follows a rst order degradation kinetic

process [48], where the decrease in Mn due to cleavage of the main chain starting at the ester bonds and is expressed by Equation (10):

Mnt2 Mnt1 $ek$t

(10)

where Mn(t1) and Mn(t2) are the number average molecular weight of the samples at time 1 and 2, respectively; and k is the hydrolysis degradation rate in d1. Tsuji and Nakahara reported k values of 2.6 103 d1 for amorphous PLA lms hydrolyzed at pH 7.4 in phosphate-buffered solution at 37  C [49]. Applying the initial PLA Mn of 90.6 2.3 (Table 1) to Equation (10) would result in a 23% reduction in Mn of the samples after 100 days at 37  C. In the present study, a 44% reduction in Mn was obtained after 100 days at 43  C. Makino et al. [50] reported a hydrolysis activation energy (DEh) for PLA in water between 83.3 and 83.7 kJ mol1 at a temperature range of 2145  C. Using DEh of 83.7 kJ mol1 to calculate a new k value at 43  C according to the Arrhenius equation (k43 C 4.8 103d1), we obtain an Mn reduction of around 38%, which is closer to the 44% reduction obtained in this study for the PLA and PLA-BHT lms submerged in water at 43  C for 100 days. The remaining difference can be attributed to acidication of the solvent as PLA hydrolyzes, which accelerates the hydrolysis rate [49]. Although the Mn and Mw of the PLA and PLA-BHT lms were reduced, BHT was not released to water after 100 days due to the very low solubility of BHT in water. PLA lms with added BHT could protect the PLA; however, PLA-BHT functional membranes have the most potential for release of antioxidant in non-water environments. 10. Conclusions Poly(94 L-lactic acid) lms compounded with 0.79 0.05 wt.-% of BHT were produced with no effect on oxygen and water barrier properties, thermal properties, crystallinity and Mw and Mn. The PLABHT lms showed an

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8% reduction of the tensile strength. The release of BHT from PLA lms into ethanol 95% followed Fickian behavior with D values between 2.95 1011 and 1.9 109 cm2 s1. The activation energy of the diffusion of BHT was 164.7 27.7 kJ mol1. No release of BHT in water at 13, 23, and 43  C for 100 days was detected. The release rate of BHT from the PLA lms in fractionated coconut oil was much lower than into ethanol 95% (3.91 and 13.2% released at 23 and 43  C, respectively after 100 days of storage). PLA and PLABHT lms stored in water at 43  C hydrolyze showing a reduction of 44% in Mn after being stored for 100 days. Acknowledgments This study was partially funded by the CFPPR (SoP, MSU) and from CONACYT (SNI-Lic-2008-102234, 2008-CB106224), Mxico. We gratefully acknowledge Elizabeth Peralta, Sukeewan Detyothin, Thitisilp Kijchavengkul, and Dharmendra Mishra for their help. Soto-Valdez thanks the Fulbright-Garca Robles Program for supporting her work at MSU. The authors thank Steven Abbott for helping with the HSPiP software. References
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