Nadine Tennabc,
Nadège Follainabc,
Kateryna Fatyeyeva*abc,
Fabienne Poncin-Epaillardd,
Christine Labrugèreef and
Stéphane Maraisabc
aNormandie Univ, France
bUniversité de Rouen, PBS, Bd. Maurice de Broglie, 76821 Mont Saint Aignan Cedex, France. E-mail: kateryna.fatyeyeva@univ-rouen.fr
cCNRS, UMR 6270, FR 3038, Bd. Maurice de Broglie, 76821 Mont Saint Aignan Cedex, France
dLUNAM Université, UMR 6283 CNRS, Institut des molécules et matériaux du Mans, Département PCI, Av. Olivier Messiaen, 72085 Le Mans Cedex, France
eCNRS, Université Bordeaux, ICMCB, UPR 9048, 33600 Pessac, France
fCeCaMa, Université Bordeaux, ICMCB, 33600 Pessac, France
First published on 10th December 2013
Different hydrophobic plasma treatments (CF4, CF4/H2, CF4/C2H2, tetramethyl silane (TMS)) were applied to the poly(lactic acid) (PLA) film in order to improve its water and oxygen barrier properties. The plasma parameters, such as power, gas flow and treatment time, were optimized according to the water contact angle measurements. X-ray photoelectron spectroscopy measurements revealed the presence of either fluorine (CF, CF2, CF3) or silicon (SiOxCy) functional groups on the film surface after the fluorinated or TMS plasma treatments, respectively. The thermal properties of the treated PLA films were studied by means of the differential scanning calorimetry (DSC) measurements and were found not to be influenced by the plasma treatment. The water permeability measurements showed an improvement of the PLA barrier properties as a result of all plasma treatments used and, particularly, after CF4/C2H2 plasma. The water vapour sorption measurements confirmed well the improvement of the water barrier properties by the reduction of the water solubility. No impact of the plasma treatment on the oxygen barrier properties of the PLA film was observed, even at high relative humidity (up to 90%).
The biobased materials are divided into three families: (i) the polymers extracted directly from the biomass, such as the starch and the cellulose; (ii) the polymers prepared by a classical synthesis reaction from monomers based on the biomass, such as poly(lactic acid) (PLA); (iii) the polymers produced from natural or genetically modified micro-organisms, such as poly(hydroxyalkanoates) (PHA).
PLA is a linear aliphatic polyester (Fig. 1), synthesized from the lactic acid, which is derived from renewable resources by the bacterial fermentation of carbohydrate,3 that means it is a biodegradable and biocompostable polymer. Historically, the PLA application was limited to biomedical and pharmaceutical fields.4,5 Recently, PLA was approved by Food and Drug Administration (FDA) which authorizes its direct contact with the biological fluid and with the food. So, PLA was used for packaging.6–8 PLA becomes increasingly used as a biodegradable polymer due to its high mechanical strength and easy processability compared to other biopolymers.9 It is important to note that oxygen, water, carbon dioxide and nitrogen barrier performances of PLA are lower than those of poly(styrene) (PS), but higher than those of poly(ethylene terephthalate) (PET).4–6
However, the main drawback of PLA is its easy degradation, mainly caused by the hydrolysis process of the ester bonds under the humid conditions. This disadvantage limits the PLA application in the packaging industry. In order to overcome this problem and to improve the mechanical, barrier and adhesion properties of PLA, different solutions have been already proposed. One of them is the melt blending with different types of plasticizer (lactide, oligomer, glycerol),4,7 natural fibers,10 with stabilizing agents (peroxides),6 or with other polymers, for example poly(caprolactone) (PCL), poly(3-hydroxy butyrate) (PHB)7 or polyphosphazene.11 The other widely used methods are the incorporation of nanoparticles4 and the surface treatments, for example, the fluorination with perfluoropolyether (PFPE).12 Each of these methods has its own advantages and limitations depending on the type of PLA and its further application.
The plasma treatment appears to be a suitable solution, since it is an environmental friendly technique (sterile dry chemistry). The treatment time is short that favours its industrial application. Besides, the plasma treatment induces a surface modification without affecting the bulk properties.13 However, in plasma chemistry several different elementary reactions (degradation, polymerization, crosslinking, etc.) can occur simultaneously; therefore the choice of the plasma parameters is a key feature of the plasma treatment. The PLA films treated by the plasma are, in most cases, intended for biological applications in order to enhance the adhesion between the cells and the PLA film and to improve the cell growth.14–19
It is known that the packaging material requires certain mechanical strength and special physical, chemical and biological properties, such as barrier protection, transparency, safe food contact, etc. Barrier properties depend essentially on the biochemical reactions taking place in food, mainly on its respiratory activity, i.e. on the reaction between sugar and oxygen resulting in forming carbon dioxide and water. In order to increase the shelf life of food, the respiratory intensity should be decreased, that can be obtained by moderating the water permeability and/or by increasing the selectivity between carbon dioxyde and oxygen.
The main objective of the present research was to improve the water and oxygen barrier properties of the PLA film. The water barrier properties were improved in order to overcome the high sensibility of the PLA film to the moisture, and the oxygen barrier properties were improved in order to enhance the PLA use in packaging application. For this purpose, hydrophobic plasma treatments such as CF4, CF4/H2 and CF4/C2H2 mixtures and TMS were used. The presence of fluorine on the surface of food packaging films may have a negative part, because of its known negative effect on our health. But the matter is in the value of fluorine. That's why it is important to clarify this point. According to FDA regulations, for the content less that 0.05 mg kg−1 day−1, fluorine is considered to be beneficial for teeth: it prevents dental caries.20 But with the content more than 2 mg kg−1 day−1, the fluorine presence leads to undesirable effects (for example, dental fluorosis). The use of the fluorine based cold plasma treatment for the polymer film modification induces the presence of very small quantity of fluorine (a few ppm) on the film surface as the thickness of the plasma modified layer is only a few nanometers. Besides, the fluorine liberation is limited due to the covalent bonds formed between the fluorine compounds formed during the plasma treatment and the polymer surface, as the fluorine is attached by covalent bonds to the film surface.21,22 Therefore, the fluorine plasma treatment can be used for the polymer films designated for the food package application. To obtain the maximum hydrophobic effect after the plasma treatment, the optimization of the plasma conditions (power, gas flow and treatment time) as a function of the water contact angle value was investigated. The influence of different plasma treatments on the PLA surface composition was analyzed by XPS measurements. The water and oxygen permeability measurements were performed in order to determine the effect of plasma treatments on the barrier properties of the PLA films. In addition, the water vapour sorption measurements were carried out for correlating the sorption and permeation properties of the plasma treated PLA films. Finally, the thermal properties of the PLA films after the different plasma treatments were studied by means of DSC measurements to ensure the stability of the bulk properties of the PLA treated films, since the thermal properties may strongly affect the barrier properties.
![]() | (1) |
The experimental sorption isotherms were fitted to Park's sorption isotherm model that supposes the association of three mechanisms: the specific sorption on special sites (Langmuir's mode) at low water activity aw (aw < 0.2); the non-specific sorption (Henry's law) for water activity range up to 0.5 and the water molecule aggregation at high water activities (aw > 0.5).27,28 Thus, Park's model comprises three terms with five parameters to be defined:
![]() | (2) |
The parameters of Park's model were calculated using the non-linear regression analysis by Table Curve 2D® software. The mean relative deviation modulus E was defined by the equation:
![]() | (3) |
The sorption data were used to calculate the diffusion coefficient D, which is a measure of the ability of the water molecules to move through the polymer film. In order to determine the diffusion coefficient, Fick's second law must be solved, which depends on geometry and concentration conditions.30 For a thin film geometry, in which diffusion from the edges of the film can be neglected and assuming a constant diffusion coefficient, the total mass sorption of the water can be described by:30
![]() | (4) |
![]() | (5) |
The change of the water contact angle values for the PLA film after CF4 plasma treatment as a function of the plasma parameters is shown in Fig. 2. The water contact angle for the untreated PLA film is about 76 ± 2°. The increase of the RF power leads to an increase of the water contact angle (Fig. 2a). This result can be explained by the fact that the initial RF power increase to 10 W provokes the dissociation of the plasma species in the reactor that, in its turn, enhances the functionalization effect. The further increase of the RF power does not lead to significant changes in the water contact angle value and almost constant value is observed starting from 15 W (110 ± 2°) due to a more pronounced effect of degradation. Under such working conditions (CF4 flow = 25 sccm and 10 min of the treatment time), the compromise between the functionalization and degradation effects was reached at 15 W.
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Fig. 2 Water contact angle of the PLA surface treated by CF4 plasma as a function of (a) RF power, (b) gas flow and (c) treatment time. |
The variation of the water contact angle value as a function of CF4 flow for the PLA film shows an inverted parabola dependence with the maximum value of about 119 ± 2° for 20 sccm (Fig. 2b). The decrease of the water contact value to 100 ± 2° was observed for the further CF4 flow increasing (over 20 sccm) due to the degradation process on the PLA surface. Consequently, CF4 flow less than 20 sccm favours the functionalization character of the plasma treatment. It is known that the degradation effect of CF4 plasma process is caused by the presence of the atomic fluorine in the plasma phase.23,32,33 Therefore, one may suppose that the contribution of the degradation process during the plasma treatment increases with the gas flow increase as the concentration of the atomic fluorine grows.
The increase of the plasma duration to 10 min revealed an increase of the water contact angle value up to 118 ± 2° (Fig. 2c). The longer treatment had only small effect on the water contact angle since a practically constant value of the water contact angle was obtained. The slight decrease of the water contact angle value observed at the beginning of the treatment (Fig. 2c) may be associated with the so-called cleaning of the PLA surface, i.e. the removal of the surface impurities.31 The optimum conditions for CF4 plasma treatment that correspond to the highest water contact angle value are summarized in Table 1.
Treatment | RF power (W) | Gas flow (sccm) | Treatment time (min) | Content of H2 or C2H2 (%) |
---|---|---|---|---|
CF4 plasma | 15 | 20 | 10 | — |
CF4/H2 plasma | 15 | 18/2 | 10 | 10 |
CF4/C2H2 plasma | 15 | 19/1 | 10 | 5 |
TMS plasma | 50 | 10 | 2 | — |
To limit the degradation effect during CF4 plasma process, different solutions may be found in the literature.31–33 D'Agostino proposed to add hydrogen to the fluorine plasma in order to combine the atomic fluorine into stable HF molecules.31 Also, the influence of the acetylene addition to the CF4 plasma was studied by Jacobsohn et al.,33 as it is known that the presence of acetylene in plasma phase allows the creation of a compact tridimensionnel network which plays an important role in the barrier properties.35–37 The addition of H2 and C2H2 gases to CF4 plasma was studied in the case of poly(ethylene-co-vinyl alcohol) (EVOH) films with different content of the ethylene groups (29 (EVOHDT29) and 44 (EVOHAT44) mol%) and quite satisfactory results were obtained.23 It was found that the best barrier improvement factor for EVOHAT44 film was obtained after CF4 plasma treatment (about 28%) and in the case of EVOHDT29 film – after CF4/C2H2 plasma treatment (about 25%). The established difference between the effects of the plasma treatment on EVOH films was related to the polymer film composition, i.e. to the content of ethylene and hydroxyl groups, and the crosslinking reactions produced during the plasma treatment.
To reduce the degradation effect and to improve the hydrophobicity of the PLA films, H2 and C2H2 gases were added to CF4 plasma phase (Fig. 3). The water contact angle value decreases after the introduction of H2 (Fig. 3a) or C2H2 (Fig. 3b) gases to CF4 plasma. This fact can be explained by the formation of the stable HF molecules and, thus, by the decrease of the fluorine species in the plasma phase. The similar results were found by Montazer Rahmati et al. in the case of polyethylene films treated by the mixture of CF4 with H2.32 Table 1 presents the optimized conditions for CF4/H2 and CF4/C2H2 plasma treatments.
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Fig. 3 Water contact angle of the PLA surface as a function of H2 (a) and C2H2 (b) content in CF4 plasma: RF power = 15 W, treatment time = 10 min. |
Transparent materials such as silicon oxide (SiOx) and silicon nitride (SiNx) deposited onto the polymer substrate were widely used as gas barrier films.21,38–40 In the case of such organic/inorganic barrier coating, the inorganic oxide layer acts as a diffusion barrier to water vapour and/or oxygen permeation. The defects of this barrier inorganic layer are covered by the polymer, thus improving the barrier performance of the composite film. Different organosilicon reactants were used for this purpose, for example, hexamethyldisiloxane (HMDSO),39,41 the mixtures of HMDSO and ammonia38 or of tetramethoxysilane and oxygen,42 etc. In the case of using TMS as a silicon source, the presence of hydrophobic groups, such as SiMe4+, SiMe3+, SiMe2+, SiMe3˙,34,43 generated by the dissociation of TMS molecules, induces a hydrophobic character of the surface after the plasma treatment.
The activation of the substrate surface is usually required in order to increase the effect of the liquid precursor use (TMS).41 Such pretreatment activation may be performed by an inert gas, like Ar or He. A pure inert gas does not contain any chemically reactive species and normally leads to radical formation, crosslinking or double bond formation on the polymer surface. In our case, Ar plasma pretreatment during 2 min was used in order to activate the PLA surface before TMS plasma as it is known that Ar plasma exposure always leads to a fresh surface for the PLA film.44 The water contact angle value as a function of the RF power is shown in Fig. 4. As one can see, practically no variation of the water contact angle is observed up to 30 W. Thereafter, the significant improvement of the film hydrophobicity was observed – the water contact angle value increased from 76 ± 2° to 96 ± 2° at 50 W. The observed water contact angle variation may be explained by the changes of the surface chemical composition.40,42 Further increase in the RF power value did not change water contact angle (Fig. 4), meaning that 50 W might be taken as the optimum value of the RF power (Table 1).
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Fig. 4 Water contact angle of the PLA surface treated by TMS plasma as a function of RF power: flow = 10 sccm, treatment time = 2 min. |
For further investigations, the PLA films treated under the optimum plasma conditions (Table 1) were taken.
Atomic percentage | Atomic ratio | |||||||
---|---|---|---|---|---|---|---|---|
C | O | F | Si | Other | O/C | F/C | Si/C | |
PLA | 59.6 | 40.4 | — | — | — | 0.67 | — | — |
Treated by CF4 plasma | 46.0 | 21.0 | 33.0 | — | — | 0.46 | 0.72 | — |
Treated by CF4/H2 plasma | 52.1 | 28.7 | 13.9 | 2.2 | 1.3 | 0.55 | 0.27 | 0.04 |
Treated by CF4/C2H2 plasma | 46.0 | 14.5 | 36.9 | 2.6 | — | 0.31 | 0.80 | 0.06 |
Treated by TMS plasma | 59.5 | 30.6 | — | 9.9 | — | 0.51 | — | 0.17 |
After all plasma treatments, the O/C atomic ratio decreases, indicating that the incorporation (grafting) of the fluorinated or silicon functional groups occurs on oxygen atoms of PLA (Fig. 1). Besides, the fluorine plasma treatments (CF4, CF4/H2, CF4/C2H2) introduce a significant amount of fluorine on the PLA surface (Table 2). To obtain a better insight into the chemical bonds on the PLA surface, the fitting of the high resolution spectra was performed (Fig. 5). The high resolution C1s spectrum for the untreated PLA film (Fig. 5a) may be decomposed into seven components according to the PLA composition (Fig. 1): the hydrocarbonated structure with C–H bonds (284.6 eV), C neighbouring to C–OH (285.3 eV), –C–OH (286.0 eV), –CO (287.1 eV), –COO− (288.3 eV) and O–C
O (289.9 eV) groups.13,19,44,45
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Fig. 5 High resolution C1s XPS spectra of the PLA films before (a) and after plasma treatments: (b) CF4 plasma, (c) CF4/H2 plasma, (d) CF4/C2H2 plasma, (e) TMS plasma. |
During the plasma treatment, active plasma species attack the polymer surface that leads to the incorporation of additional functional groups. As one can see from Table 2, the fluorine treatment of PLA results in a substantial amount of fluorine at the surface. In this case, the spectra become more complex and the appearance of the fluorinated group peaks may be observed at 290.9, 291.9 and 292.9 eV for CF-, CF2- and CF3-groups, respectively (Fig. 5b–d).22,23,46,47 The decomposition of the high resolution F1s spectra obtained for the PLA surface after the fluorine plasma treatment (Fig. 6a–c) also reveals the presence of the fluorinated groups at 688.3 eV, 686.9 eV and at 685.4 eV.22,47 Besides, it should be noted that the peak attributed to the presence of CF2-groups on the PLA surface (around 686.8 eV) is the highest one (Fig. 6a–c). These results correlate well with the water contact angle measurements, as it is known that CF2 groups make the main contribution to the hydrophobic character of the film.32,33 The presence of the peak at 285.4 eV was observed on the high resolution C1s spectrum after TMS plasma treatment (Fig. 5e). At the same time, the binding energies of silicon chemical bonds locate at 101.0 eV for C3–SiO, at 102.4 eV for C2–SiO2 and at 104.0 eV for SiO4 (Fig. 6d). The deposition of the inorganic SiOxCy layer on the PLA surface results in the decreasing of the oxygen content and in the presence of ∼10 at.% of silicon (Table 2).
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Fig. 6 High resolution F1s and Si2p XPS spectra of the PLA films after plasma treatments: (a) CF4 plasma, (b) CF4/H2 plasma, (c) CF4/C2H2 plasma, (d) TMS plasma. |
Tg (°C) | ΔHC (J g−1) | Tm (°C) | ΔHm (J g−1) | XC (%) | |
---|---|---|---|---|---|
PLA | 56.7 ± 2.0 | 33 ± 3 | 150 ± 1 | 34 ± 3 | 1 ± 3 |
Treated by CF4 plasma | 56.9 ± 2.0 | 28 ± 3 | 144 ± 1 | 33 ± 3 | 6 ± 3 |
Treated by CF4/H2 plasma | 57.2 ± 2.0 | 29 ± 3 | 151 ± 1 | 35 ± 3 | 6 ± 3 |
Treated by CF4/C2H2 plasma | 56.6 ± 2.0 | 29 ± 3 | 151 ± 1 | 32 ± 3 | 4 ± 3 |
Treated by TMS plasma | 58.6 ± 2.0 | 32 ± 3 | 151 ± 1 | 33 ± 3 | 1 ± 3 |
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Fig. 7 The time evolution of the water contact angle of the PLA surface after plasma treatments: (□) CF4 plasma, (◊) CF4/H2 plasma, (○) CF4/C2H2 plasma, (Δ) TMS plasma. |
P (Barrera) | Diffusion coefficient at J/Jst = 0.24 DI × 1010 (cm2 s−1) | Diffusion coefficient at J/Jst = 0.62 DL × 1010 (cm2 s−1) | Mean integral diffusion coefficient 〈D〉 × 1010 (cm2 s−1) | Plasticization factor γCeq | Barrier improvement BI (%) | |
---|---|---|---|---|---|---|
a 1 Barrer = 10−10 cm3(STP) cm cm−2 s−1 cmHg−1. | ||||||
PLA | 2030 ± 32 | 94 ± 15 | 117 ± 18 | 187 ± 37 | 2.0 ± 0.1 | |
Treated by CF4 plasma | 1688 ± 47 | 162 ± 32 | 227 ± 42 | 428 ± 103 | 3.2 ± 0.1 | 17 |
Treated by CF4/H2 plasma | 1670 ± 36 | 107 ± 24 | 140 ± 25 | 246 ± 43 | 2.6 ± 0.1 | 18 |
Treated by CF4/C2H2 plasma | 1608 ± 78 | 103 ± 4 | 136 ± 9 | 242 ± 34 | 2.7 ± 0.7 | 21 |
Treated by TMS plasma | 1910 ± 126 | 112 ± 18 | 144 ± 30 | 255 ± 73 | 2.5 ± 0.6 | 6 |
As one can see from Fig. 8a, all plasma treatments result in the decreasing of the water permeability (the steady state of water permeation flux decreases), especially after CF4/C2H2 plasma. These results are in good agreement with the water contact angle (Fig. 2–4) and XPS (Table 2) measurements. Indeed, CF4 plasma induces an important hydrophobic effect (the increasing of the water contact angle from 76° to 120° and the presence of 33 at.% of fluorine on the PLA surface). However, the presence of the atomic fluorine favours the degradation (etching) effect, which negatively impact the barrier properties.23,49 The addition of H2 to CF4 plasma will promote the decrease of the degradation effect of the atomic fluorine, but, in its turn, will give a slightly hydrophilic character to the treated surface.32 In the case of CF4/C2H2 plasma, the hydrophobic character of CF4 plasma is strengthened by the crosslinking effect of acetylene.33,35–37 Really, in this case the higher fluorine content was obtained on the PLA surface (∼37 at.%, Table 2). Therefore, the treatment by the mixture of CF4/C2H2 seems to be the most efficient, as in this case the barrier improvement (BI) is about 21% (Table 4). For comparison, Chaiwong et al. have obtained the BI that equals to 14% for the PLA film treated by SF6 plasma.49
The comparison of DL and DI coefficients (Table 4) shows that DL value is higher than DI value for all PLA films. As the former value corresponds to a latter period of the transient state (J/Jst = 0.62), the smaller DI value means that the water diffusion increases during the permeation process. Generally, such diffusion increase is attributed to the plasticization of the material by water which leads to an increase of the material free volume. All permeation curves were fitted to the well known exponential law of diffusion23,30
D = D0eγC, | (6) |
Therefore, one can deduce that the decrease of the permeability can be explained by the reduction of the affinity between the water molecules and the polymer surface due to the presence of hydrophobic groups on the treated surface, i.e. by decreasing the solubility coefficient. To valid this hypothesis the water vapour sorption measurements were performed.
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Fig. 9 Water vapour sorption isotherms for the PLA films before (●) and after plasma treatments: (□) CF4 plasma, (◊) CF4/H2 plasma, (○) CF4/C2H2 plasma, (Δ) TMS plasma. Solid lines are the best fit to Park's model (eqn (2)). |
The water sorption measurements performed for the plasma treated PLA films reveal the same sorption behaviour as the untreated PLA film (Fig. 9). The obtained isotherms clearly show that all plasma treatments reduce the water sorption capacity of PLA in the whole water activity range. However, even if the moisture resistance is enhanced, the plasma treatment of PLA has not strongly reduced the ability of PLA to absorb and accept water. The low sensitivity of PLA to the water (∼1%) and the small thickness of the plasma treated layer may explain not very significant barrier improvement.
As the increase in aw is accompanied by a nonlinear increase in water content, the experimental water sorption isotherms were fitted according to Park's model (eqn (2)). The results presented in Table 5 confirm that Park's model is a good representation of the experimental data – the mean deviation modulus E values (eqn (3)) are ranging from 2.5 to 9.6% that validate the performed fit. Consequently, the water sorption behaviour can be understood by analyzing the constants of Park's model. Mathematical fitting of the sorption data to eqn (2) has shown the decrease of AL value for all plasma treated PLA films (Table 5). This value represents the Langmuir's capacity constant related to the concentration of specific sites on which water molecules can be sorbed. The decrease of AL value indicates the reduction of the surface solubility of plasma treated surfaces for water molecules (Fig. 9). The reduction of this adsorption (Langmuir's mode) testifies to the presence of the plasma grafted hydrophobic groups on the binding sites. In the case of PLA, the specific sites of sorption are mainly the –OH groups (Fig. 1). This result is in good agreement with the XPS analysis, i.e. with the decrease of the oxygen atomic concentration after the plasma treatments (Table 2).
AL | KH | Kagr | n | E (%) | |
---|---|---|---|---|---|
PLA | 0.0830 | 0.42 | 1403 | 13 | 2.5 |
Treated by CF4 plasma | 0.0003 | 0.42 | 2054 | 13 | 7.9 |
Treated by CF4/H2 plasma | 0.0090 | 0.40 | 2259 | 12 | 9.6 |
Treated by CF4/C2H2 plasma | 0.0020 | 0.41 | 2086 | 13 | 5.3 |
Treated by TMS plasma | 0.0035 | 0.45 | 1027 | 13 | 4.8 |
As one can see from the results in Table 5, the found KH and n values for the untreated and plasma treated PLA films are quite close that means that Henry’s law (i.e. non-specific absorption) and water clustering components were practically not influenced by the plasma treatments. The change of the water sorption behaviour of the plasma treated PLA films is in accordance with the result obtained by Chaiwong et al. for the PLA film treated by SF6 plasma.49 The authors ascertained that the water absorption time increased twice after the plasma treatment due to the presence of the fluorinated functional groups on the PLA surface.
In conclusion one can say that the hydrophobic plasma treatment by CF4, CF4/H2, CF4/C2H2 and TMS makes the entrance of the first water molecules into the polymer structure difficult, thus affecting Langmuir's mode (the decrease of AL value (Table 5)). Therefore, the reduction of the water permeability can be caused by the decrease of the water solubility. In other words, the decrease of the water permeation flux occurs after the plasma treatment as if the total surface of the film, which is in contact with water, is reduced because of the presence of hydrophobic groups. From the moment when the first water molecules penetrate into the polymer and as aw value increases, the PLA film starts to swell, opening up new (deeper in the film thickness) sites for water to adsorb. It should be also noted that the acceleration of the sorption process was observed at the highest water activity (aw = 0.95) for the PLA films treated by CF4/H2 and TMS plasma (Fig. 8). It means that the access of the water molecules into the polymer becomes easier and the water aggregation increases. This phenomenon cannot be explained clearly for the moment.
The diffusion coefficient (eqn (5)) can more directly reflect the effect of the performed plasma treatment on the transport mechanism of the water molecules in the PLA films. Fig. 10 shows the variation of the water diffusion coefficient as a function of water vapour activity for untreated PLA film as well as for all plasma treated PLA films. Three domains may be distinguished from the experimental data represented in the semi-logarithmic scale either for untreated PLA or for the plasma treated films. At low water activity (aw ≤ 0.3) the increase of the diffusion coefficient is observed due to the plasticization effect.30 Indeed, the absorption of water molecules by the specific sites leads to the free volume increase in PLA and, thus, improves the mobility of the water molecules. In the case of the plasma treated PLA films the increase of the diffusion coefficient is less pronounced because of the plasma grafted hydrophobic groups' presence on the specific sites (Langmuir's contribution). At medium water activity (0.3 < aw < 0.6) the diffusion coefficient remains practically constant (Fig. 10). For more hydrophilic polymers, e.g. derivatives of cellulose, the plasticization effect induced by water molecules is usually observed for a larger water activity (0 < aw < 0.5).30
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Fig. 10 Influence of the water activity on the diffusion coefficient for the PLA films before (●) and after plasma treatments: (□) CF4 plasma, (◊) CF4/H2 plasma, (○) CF4/C2H2 plasma, (Δ) TMS plasma. |
A significant decrease of the diffusion coefficient is observed for aw > 0.5 (Fig. 10). Such variation of the diffusion coefficient with the water activity may be explained by the presence of water aggregates which are formed during the water vapour sorption process.23,30 Thus, the reduction of the mobility of the water molecules is observed. Besides, the variation of the diffusion coefficient with the water activity increase is the same for both untreated and plasma treated PLA films.
The plasticization phenomenon has been revealed by both sorption and permeation measurements (Table 4 and Fig. 10). Moreover, it is interesting to note that the sorption kinetic measurements have also revealed the aggregation phenomenon. It is important to remind that the boundary conditions are different for sorption and permeation processes. It means that the PLA film is not under the same experimental conditions, i.e. both faces of the polymer film are in contact with the water vapours during the permeation measurements whereas only one film face is in contact during the sorption measurements, so that the water concentration gradient is different. Therefore, as the aggregation of water molecules is considered as rather slow process, so mostly it may be observed by the sorption measurements.
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Fig. 11 Relative humidity effect on the oxygen permeability of the PLA films before (●) and after (○) CF4/C2H2 plasma treatment. |
The oxygen permeability coefficient value measured for the untreated PLA film (0.2–0.3 Barrer) is close to that reported in the literature – 0.31–0.61 Barrer depending on the polymer structure.5 The oxygen permeability of the PLA film is not really affected by the RH (Fig. 11). Only a slight decrease of the oxygen permeability is observed at RH = 50% following by the oxygen permeability increase with the further RH increase. Two explanations of this phenomenon can be found in the literature. The first one is that such decrease of the oxygen permeability at RH = 50% may be attributed to the facility of the water molecules to faster occupy the free volume in the polymer matrix in comparison with the oxygen molecules.53 This will decrease the diffusion pathway of the oxygen molecules and, consequently, the oxygen permeability will be reduced. The second one explains the observed decreasing of the oxygen permeability by the antiplasticization effect.54 In this case the water molecules fill the available free volume in the amorphous region of the polymer, thus strengthening the intermolecular hydrogen bonding across the free volume. Thus, the water molecules hinder the polymer chain mobility at this RH level and reduce the diffusion of the oxygen molecules. At higher RH levels (>50%), the water molecules form agglomerates inside the PLA film by increasing the water concentration in the polymer that leads to the increase of the oxygen permeability in the PLA film.
The oxygen permeability values for the untreated and plasma treated PLA films are found to be of the same order of magnitude even at high RH (90%) (Fig. 11). Besides, the PLA film treated by CF4/C2H2 plasma exhibits similar oxygen barrier performance compared to the untreated PLA film, i.e. the decrease of the oxygen permeability up to 50% RH with its further increase. Such a result is not very surprising as the water plasticization effect is not vanished even after the plasma treatments (Fig. 8 and 10). Therefore, in order to reduce the oxygen permeability, a decrease of the plasticization should be obtained. For this purpose, the successive plasma treatment will be the subject of further investigation.
The increase of the water barrier properties of PLA after all plasma treatments was shown by the water permeability measurements. The highest improvement was obtained after CF4/C2H2 plasma treatment – up to 21%. The barrier effect was explained by the hydrophobic character of the grafted fluorinated groups and by the crosslinking reaction caused by the presence of C2H2 in the plasma phase. The analysis of the water permeation and sorption measurements confirmed that the decrease of the water permeability was mainly due to the decrease of the solubility inside the plasma treated PLA films for the water molecules. However, no significant effect of the plasma treatment on the oxygen barrier properties of the PLA films was established, even at high RH levels. This result may be explained by the water plasticization and the formation of water clusters after the plasma treatment.
Thus, one can conclude that the hydrophobic plasma treatment is the effective means to improve the water barrier properties of the PLA films.
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