The influence of moisture content on the polymer structure of polyvinyl alcohol in dispersion barrier coatings and its effect on the mass transport of oxygen

Journal of Coatings Technology and Research, Jun 2017

This paper presents a study of the effect of moisture on the gas permeability of polyvinyl alcohol (PVOH) and PVOH–kaolin dispersion barrier coatings. The oxygen permeability was measured at different humidity levels, and the material properties were characterized under the same conditions: polymer crystallinity, kaolin concentration, and kaolin orientation were all evaluated. The experimental results revealed that the water plasticizes the PVOH material of the coatings, and the presence of kaolin filler is unable to affect such behavior significantly. The PVOH crystallinity was affected drastically by the humidity, as water melts polymer crystallites, which is a reversible process under removal of water. The permeability data were analyzed using a thermodynamic-based model able to account for the water effect on both the solubility of the gas and the diffusivity coefficients in the polymer and composite. The results showed good agreement between the model’s predictions and the experimental data in terms of the overall permeability of the material.

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The influence of moisture content on the polymer structure of polyvinyl alcohol in dispersion barrier coatings and its effect on the mass transport of oxygen

The influence of moisture content on the polymer structure of polyvinyl alcohol in dispersion barrier coatings and its effect on the mass transport of oxygen A˚ sa Nyflo¨ tt 0 1 C¸ ag˘ lar Meric¸er 0 1 Matteo Minelli 0 1 Ellen Moons 0 1 Lars Ja¨ rnstro¨ m 0 1 Magnus Lestelius 0 1 Marco Giacinti Baschetti 0 1 0 C ̧ . Meric ̧er, M. Minelli, M. G. Baschetti Department of Civil, Chemical, Environmental and Materials Engineering , Alma Mater Studiorum , University of Bologna , 40131 Bologna , Italy 1 E. Moons Department of Engineering and Physics, Karlstad University , 651 88 Karlstad , Sweden This paper presents a study of the effect of moisture on the gas permeability of polyvinyl alcohol (PVOH) and PVOH-kaolin dispersion barrier coatings. The oxygen permeability was measured at different humidity levels, and the material properties were characterized under the same conditions: polymer crystallinity, kaolin concentration, and kaolin orientation were all evaluated. The experimental results revealed that the water plasticizes the PVOH material of the coatings, and the presence of kaolin filler is unable to affect such behavior significantly. The PVOH crystallinity was affected drastically by the humidity, as water melts polymer crystallites, which is a reversible process under removal of water. The permeability data were analyzed using a thermodynamicbased model able to account for the water effect on both the solubility of the gas and the diffusivity coefficients in the polymer and composite. The results showed good agreement between the model's predictions and the experimental data in terms of the overall permeability of the material. Mass transport; Permeability; Modeling; Barrier coating; Moisture; Kaolin; PVOH Introduction Gas barriers are often employed to hinder the permeation of molecules through a material. In order to achieve the desired performance of the barrier, it is important to understand the mechanism of mass transport of the relevant species through the material.1,2 Filled polymer layers can be used as barrier coatings in the packaging industry. In this end-use application, it is important to be able to regulate the mass transport of, e.g., moisture, grease, and gases. Among the others, oxygen may be detrimental to the quality of packaged food, especially if the food contains lipids.3–5 Although the environmental conditions may affect the barrier performances over time, these should be withstood for the entire shelf life of the packaged product. It is essential that the material properties, and all factors affecting gas permeability, are well understood for the development of novel efficient barrier materials and the proper design of the existing ones. Polymeric barrier materials are typically filled by impermeable inorganic fillers to improve their barrier performance.6,7 Polymer-based composite materials can be prepared by dispersion, interlamellar polymerization, or melting to provide not only enhanced barrier properties, but also better mechanical behavior and thermal stability.8,9 However, significant research efforts are still being devoted to the development of materials that can improve the performance and stability of the composite.10,11 The performance of the oxygen barrier depends on the nature of polymer and fillers used, as well as on processing conditions.12,13 For example, the suspensions used in dispersion coatings are usually water soluble, which makes them sensitive to moisture. Therefore, the qualitative and quantitative evaluation of the effect of the different processing parameters and environmental conditions on coating properties and performances is of paramount importance in obtaining a clear view of their performance and suitability for industrial development. The permeation of gas through a barrier coating is affected by polymer properties, such as chain mobility, crystallinity, and free volume cavities.14 In the case of filled polymeric layers, the tortuous permeation pathways within the polymer are affected by the volume fraction and distribution (shape, size, and concentration) of the filler. Among the materials available in the field of dispersion coatings, polyvinyl alcohol (PVOH) is one of the most important; indeed, it has often been investigated alone or together with different fillers as to its suitability as a composite barrier layer.7,15 PVOH has good film-forming properties and is a great O2 barrier, but has the drawback of being significantly water sensitive. The addition of clay can improve the barrier properties under humid conditions: the tortuous pathways introduced to the water molecules lower interaction with the polymer phase. Recently, Nyflo¨ tt et al.16 developed a modeling approach able to describe the gas solubility and diffusivity in polymer bases systems, and also to account simultaneously for the tortuosity effect produced by the addition of layered fillers. The penetrant solubility is evaluated making use of an equation of state (EoS) based model, which represents a wellestablished effective method for calculating the solubility of gases and vapors in amorphous polymer melts or rubbers. The nonequilibrium behavior of amorphous polymers has to be accounted for using the nonequilibrium thermodynamic model for glassy polymers (NET-GP),17,18 which provides the required extension of the EoS approach below Tg. The model uses the lattice fluid EoS model by Sanchez and Lacombe19 in combination with the NET-GP approach, giving rise to the so-called nonequilibrium lattice fluid (NELF) model.17 The NELF model is able to represent the solubility of gases and vapors in amorphous glassy polymers; the lattice fluid model is combined with the simple transport model, as done previously by others.20–27 The diffusivity of the penetrants has to be analyzed too and described by an appropriate transport model. The diffusional behavior of the penetrant in the polymer matrix is related to the penetrant size and the diffusion sites available. Semicrystalline polymers force the penetrant to take a tortuous path around the often impermeable crystalline regions, which affects both diffusivity and solubility. Tortuous paths produced by platelet-like fillers, e.g., clay, have been studied extensively by many groups by analytical solutions with a simplified geometry, numerical calculations based on ordered or random structures or molecular simulations.6,28–51 The addition of filler can enhance the barrier function of polymer films since it introduces regions that are impermeable to gases, and the diffusional pathways for the penetrating molecules may be significantly enhanced. The aim of this study was to investigate the effect of moisture on the barrier properties of PVOH and PVOH–kaolin composites, namely filler dispersion, barrier structure, and barrier performance. The permeability was measured at different RH in the range of 0–80%. The barrier structure was affected by humidity and kaolin concentrations. A model was also built to describe the behavior of the materials by combining different models that are able to account independently for the effect of gas solubility, filler dispersion, polymer crystallinity, and humidity on the barrier properties of the composite material. Materials and methods Materials The barrier layer used in this study was made from PVOH (Mowiol 15-99 from Kuraray, Frankfurt, Germany) and kaolin (IMERYS, Sandersville, USA). The kaolin particles were received pretreated with sodium polyacrylate (NaPAA). The size distribution of the kaolin platelets had previously been determined to be in the range 0.1–5 lm (width and length)52; according to the supplier, the completely separated platelets had a width-/length-thickness ratio of 60 (corresponding to an aspect ratio 16, according to the definition adopted in this work: surface area of the plane divided by surface area of side surface). PET sheets (23-lm thick) purchased from HiFi Industrial Films (Hertfordshire, UK) served as the coating substrate; their even thickness and high adhesion strength to the PVOH coating made them very suitable for this purpose.53 Preparation of PVOH, kaolin dispersions and coatings PVOH was dissolved in deionized water at 95 C under gentle stirring for 1.5 h and then cooled to room temperature before film preparation or being mixed with kaolin. The kaolin clay was dispersed in deionized water by high-shear mixing to a concentration of 60 wt%. Once this process was complete, the dispersion was stirred at a lower speed for 30 min before being diluted to the concentrations required to receive the target concentration in the dry state. Finally, the pH was adjusted to 6.8. Aqueous suspensions, based on PVOH and water solutions of kaolin, were prepared and coated onto the PET films according to the procedure described below.54 The dispersion was drawn down on the PET sheets with a bench rod coater (K202 Control Coater, RK Print Coat Instruments Ltd., Royston, UK) and subsequently dried at 95 C in a heating chamber until the barrier coatings contained only 5% water. The barrier coating reached temperatures of approximately 70 C during drying, as measured by an IR temperature sensor (Thermopoint TPT 62, FLIR system AB, Danderyd, Sweden). The water content in the barrier during drying was measured with a contactless NIR moisture sensor (FIBRO MCA 1410, FIBRO System AB, Ha¨ gersten, Sweden). The dried weight proportions of the dispersions and the measured crystallinity in nonconditioned samples are given in Table 1. The thickness was measured mechanically using a micrometer screw (Mitutoyo micrometer, ± 0.5 lm resolution, Mitutoyo Scandinavia AB, Va¨ sby, Sweden) measuring the thickness at six positions of the sample; the PET substrate was found to have a thickness of 22 ± 0.1 lm, and that of the coating resulted 4 ± 2 lm (measured together with PET). Permeability methods Permeability measurements were taken in two different setups (manometric permeometer and ambient oxygen ingress rate, described below). In all of the methods, a sample was introduced and monitored until steady-state permeation was reached. The uncertainty of the steady-state permeability was estimated as being less than 10% of the reported values, which then includes both the error from the permeability measurement and the coating thickness. Figure 1 shows the layout of the pressure-based permeometer, used to measure the oxygen permeability at various humidity levels from dry to about 80% RH.55,56 The system measures the amount of gas permeated through the polymer sample by monitoring the pressure increase in a calibrated volume compartment ASTM.57 The experimental procedure (Fig. 1) began by mounting the specimen in the sample holder and carefully, under vacuum, removing the residual water and gases absorbed in the sample for a minimum of 2 days in order to rid the polymer of all the residual substances it had absorbed. In the case of the dry experiments, the system was then ready for the tests. The upstream compartment was filled with the desired gas, and the pressure increase was monitored in the downstream gas resulting from permeation across the sample. In case of the humid gas experiments, the sample was equilibrated to the desired RH by exposing 100.0 98.9 97.0 95.0 89.8 80.0 it to pure water vapor at the correct pressure. Then a gas stream at the same RH was fed to the upstream side of the film, and the pressure downstream was monitored, as in dry experiments. More information on the two experimental setups, as well as the measuring techniques, can be found elsewhere.55,56 The ambient oxygen ingress rate (AOIR) measures the oxygen increase in a cell; the humidity in the cell is controlled by a salt solution. The AOIR measurements are taken using a zirconium sensor instead of a pressure sensor.58 In this case, both sides of the cell are flushed either with air (upstream) or nitrogen (downstream). The sensor measures the increase in oxygen concentration on the downstream side, which is used to calculate the permeate flow. This setup, shown in Fig. 2, therefore uses oxygen from the atmosphere (20.9% oxygen) rather than the pure (100%) oxygen that a permeometer uses. All permeability measurements were taken at 35 C. The permeability, P, of the pressure-driven permeometer was calculated using the following expression: P ¼ dp V s dt t!1RTA Dp where V is the cell volume, T is the temperature, A is the area, p is the pressure, t is the time and s is the thickness of the sample. The permeability from the AOIR measurements was calculated according to: P ¼ dc V R T s dt t!1VgasðSTPÞ patm A where c is the concentration in the downstream compartment and patm is the difference in the partial pressure of oxygen across the sample (0.21 atm). The permeation areas and downstream volumes were A = 9.6 cm2 and V = 26.34 cm3 (dry tests) and V = 15 cm3 (humid tests) for the manometric apparatus, while and A = 5 cm2 and V = 225 cm3 for the AOIR apparatus. The oxygen permeability was measured on multilayer samples with PET substrates, and its permeability was found to equal 2.9 9 10 17 ± 0.3 mol s 1 m 1 Pa 1 (the error is given in standard deviation). The permeability of the coating only had been calculated using the well-known resistance series formula59: ð1Þ ð2Þ Data acquisition Gas Cylinder Vacuum Pump 225 mL Salt solution 225 mL Salt solution Barrier where li and Pi are the thickness and permeability of the ith layer (2 in this case, i = 1 represents PET and i = 2 represents the barrier coating). Characterization of the material Fourier transform IR spectroscopy The FTIR spectra were collected with a Thermo Nicolet FTIR iS10 spectrometer (Madison, USA) in an attenuated total reflectance (ATR) mode using a diamond crystal, which gave a 0.3-lm penetration depth at 3600 cm 1 (see Nyflo¨ tt et al.54 for further details). The orientation of the clay was determined ð3Þ Differential scanning calorimetry from the FTIR spectra. The kaolin orientation factor, j, can be calculated from the ratio of the peak intensity at 3695 cm 1 and the peak intensity at 3620 cm 1 60 thus: peak intensity 3695 cm 1 j ¼ peak intensity 3620 cm 1 : Low j is interpreted as being the long axis of the kaolin platelets orientated in the basal plane of the substrate. FTIR measurements were also taken to investigate the effect of humidity conditioning on the crystallinity of the samples based on PVOH. Several samples were first equilibrated at different RH using salt solutions, and the IR spectra that were collected were analyzed by monitoring the peaks in the region 1090–1140 cm 1. This region contains peaks ( 1096 and 1142 cm 1) related to the amorphous and crystalline phases of the materials: They were resolved with peak area fits and used to determine the crystallinity as the ratio of the two peak areas. Polymer crystallinity was also measured by a differential scanning calorimeter DSC (DSC Q2000, TA Instrument, Newcastle, USA)61: DHfðT0 /Cð% Þ¼ DHf0ðTmÞð1 TfÞ mfÞ 100 % where DHfðT0 TfÞ is the enthalpy of fusion of the sample between temperature T0 and Tf, DHf0ðTmÞ is the enthalpy of the 100% crystalline polymer and mf is the mass fraction of the filler. For PVOH, the enthalpy of the totally crystalline polymer is DHf0ðTmÞ = 138.6 J g 1.62 The crystallinity of PVOH measured by a DSC has been reported to be in good agreement with that measured by X-ray diffraction (XRD) at low water ð4Þ ð5Þ y t r e p o r p / n o i it n s s fi e e e lu lu D a a v v . o n . q E i i t t n n e e n n o i o p t p m n e m o e c o c n n c o a e re p t r u m sb u p o p f c su f o o e e e r r s r u u sa tua fp p f m re o o em lra p le s m o ite a o e m N m t s e v R p ¼ i i T p i 0 r ¼ # ji p ~q D j þ p q q 0 i r j þ q q n l h / Þ 1 ~q þ 1 Np Xj¼ 1 1ð þ Þ ln i C p / " ¼ C i S S S 9 1 8 1 ) s u o h p r o m a ( s s a l g m u i r b lii u q e n o n 1 2 , 0 2 e ) h e t n in lli i ta t s s n y ice ice irc fsep ffieo (sem o c t l y n itan ilitb icfie teop lsuo fceo l t ica tran ility m e b e n lu h e o y t i l i b u l o s e t a l u c l a c n o i t a u q E : 2 e l b a T o i t l M d o e b ,Ti Ti s m i i u y p p s S t n e n o p m o c e r u t n e n o p m o c i lt u P M e s re tt,,rruaeepeandm it,,rrsssyuepenad iitccssyupeoedba llifttyceobaoam irshponauopham iitfttrsyxehouem itysedn itftrssxhoueeum itfccfineoe litftrcaobeem ttfrroeuepahe lrrkcvepedaoom iliirubeequoESm rrsspeue iitrscden lifttcoae iccpoued iitfcono iftrcoan iitrscden itrxuem iitrrscpe trreaaem ittrceaon reeagnu iittrscem l-csoepa cL–aobm , te r a te ed te p in v te e z itsy rca be em frs em rca cu rca ry ry ra rca rag che n a m lu s lu a d a a a la a e n e h u o a o h e h in in o h v a D C N V M V C R C B B M C A S C P S ji qi qi0ri vi xi /i q ~q p D k r T v p ji E N1 i l S content61 and measured by FTIR at constant water content.52 The films were removed from the PET substrate to be preconditioned at 20, 50, and 80%RH for 8 h prior to the DSC measurements being made and placed in pans. The samples in the hermetically sealed pans were equilibrated at 35 C for 0.5 min, and the temperature was raised from 35 to 250 C at a rate of 5 C min 1, with the temperature modulated by ±0.796 C every 30 s. 20 21 22 23 24 25 26 27 Lam ¼ Ae Ea=RT LSC ¼ Lamð1 8 > >><> r sff ¼ > > >>: r a /a rs ¼ /a2 a ¼ SSnL ðin 3D) Peff ¼ ð1 Pwater p ¼ Pcomposite 1 /CÞ ða1/Þ/2ðð11þþ11==aaÞÞ4 þ pa=/4 1 þ a 1 2 ln ðp1=2/Þ/ð1ð1þþ11=a=ÞaÞ 1a/ þ pa=/4 1 þ 1a 2ln að1þ1=aÞ ðp=2Þ /C Þ2L xpi sff 1 þ ppþ21 tA 3tA 0.3 0.25 The permeability model previously described16 was used to calculate barrier performance of flake-filled semicrystalline polymer coatings. The model is now expanded further so that it can also capture the effect of humidity on mass transport in such material. The presence of water in the polymer samples can be accounted for in the thermodynamic analysis of the system, which describes the effect it has on crystallinity and diffusivity. For the sake of clarity, the model is summarized in Tables 2 and 3; Equations 9–16 are included because of the addition of the influence of water (Fig. 3). The analysis of water solubility in PVOH, based on data after Tadokoro et al.63 illustrated in Fig. 4, suggested that the addition of water induced a glass transition in the PVOH phase, even at low activity values, at the measurement temperature (T = 25 C). Since water acts as a plasticizer of PVOH,64 the mixture can be treated as being at thermodynamic equilibrium in a reasonably wide range of activities.65 The water solubility can therefore be described by the equilibrium known as the Sanchez and Lacombe equation of state (EoS). The curve obtained in Fig. 4 was used to retrieve the values of the mass fraction of water in the polymer film at the RH at which the experiments were performed: 0, 20, 50, and 80% RH. Permeometer AOIR 1 2 3 Kaolin concentration/wt% 4 5 For sake of simplicity, the mixture of PVOH and water was then treated as a single component at each specific RH: The pure characteristic parameters of this pseudocomponent were determined by the Sanchez and Lacombe EoS and the Sanchez and Lacombe mixing rules of the EoS (Equations 6–17). These parameters were evaluated and used in the calculation of the solubility of the oxygen in the film. The polymer phase at high humidity has a higher degree of mobility, which leads to the penetrant diffusing faster. This can be described by the binary Maxwell equation. Although this equation is derived at infinite dilution (when tA ! 0) and for spherical particles, it has nevertheless been proven to be useful for higher concentrations as well as for other types of particles.66–68 Results and discussion Characterization of the material The crystallinity of the various samples at different levels of RH showed values ranging from 10% to 60%, depending mainly on the concentration of kaolin, as shown in Fig. 5. The nonconditioned samples (i.e., in dry conditions) showed higher crystallinity, between 36 and 47%, and a weak dependence on the content of kaolin, Fig. 5. The conditioned samples, on the other hand, showed a decrease in crystalline content, which was particularly relevant when the kaolin had a concentration of 10% or above. A clear decrease in the crystallinity of the conditioned sample was indeed evident in this range. Interestingly, the barrier films appear to be more water sensitive when kaolin is present; larger depressions in the crystalline contents are observed at increasing RH. Humidity promotes the breakdown of crystalline regions, since water molecules diffuse into these regions and weaken the hydrogen bonds, eventually dissolving the crystals.69 The water melts polymer crystallites, which is a reversible process under removal of water. The decrease in the size of the crystalline regions caused by water was also observed clearly by the FTIR measurements, and the results of which are illustrated in Fig. 6. When crystallinity is measured by ATRFTIR, only the vibrational modes at the surface of the samples are accessed, whereas the DSC method probes the whole sample. This explains the slightly different results that were obtained by these two methods. 1E–15 1E–16 1 – aP1E–17 1 – 1 m – ls1E–18 o m / P 1E–19 1E–20 Parameter qPVOH (amorphous) MO2 L0 (amorphous PVOH) T*PVOH+water T O2 q*PVOH+water q O2 p*PVOH+water p O2 p tA Permeability The oxygen permeability of the pure coatings was evaluated using the resistance formula, and the results are given in Fig. 7. The plot presents a substantial agreement between the data obtained by different measurement techniques, even if there is a slight scattering present. The permeability measured by the two different methods is then summarized in the combined plot in Fig. 8. In the calculation of the barrier coating alone, equation (3), the permeability of PET substrate was treated independently of RH. However, it is a known fact that the permeability of oxygen through PET varies slightly with water content.70 Figure 8 shows the results of the samples containing only PVOH and the mixture of PVOH:10 wt% kaolin measured with the AOIR instrument. The permeability values at 0% RH (excluding PVOH and the mixture of PVOH:10 wt% kaolin) were measured by the manometric permeometer. As can be seen, the addition of kaolin increases the permeability of the gas compared to only PVOH, up to 50% RH. This indicates that kaolin introduces microvoids into the material, thus lowering the overall barrier effect. On the other hand, the presence of moisture increases the O2 permeability significantly, which is the result of the plasticizing effect had by the water molecules and makes the polymer chains produced by the interaction with water molecules more flexible. The overall behavior shows that an initial increase in permeability was followed by levelling at higher concentrations of kaolin except for the highest level of humidity, at Units g cm 3 g mol 1 cm2 s 1 K K kg m 3 kg m 3 MPa MPa References 60 61 This work 62 This work 62 This work 62 This work This work Fig. 9: Parity plot between the permeability determined experimentally (presented in Fig. 8) and that obtained from the model for kaolin contents of 0, 1, 3, 5, 10, and 20 wt% which no significant influence of clay loading could be detected on permeability. Although PVOH coating is a good oxygen barrier at low RH, this function is completely lost at 80%RH due to the water sensitivity of PVOH, as shown elsewhere.71–74 Modeling permeability The previous approach was modified to include the effect of humidity on the oxygen permeability model for the barrier coating. The moisture is included by adding the pseudocomponent in the solubility and the binary Maxwell equation in the diffusivity (equation 26). The parameters of the pseudocomponent, i.e., PVOH + water, are calculated according to Sanchez and Lacombe’s mixing rules.19 The parameters calculated using the Sanchez Lacombe EoS are summarized in Table 4 and used further in the permeation model. It is quite remarkable that the new model shows very good agreement with the experimental results, as illustrated in Fig. 9. Figures 5 and 6 show that the degree of crystallinity varies significantly at the different RH, and such changes need to be considered in the modeling analysis. The size of the crystallites is not explicitly considered, but only its volumetric fraction, in the hypothesis that crystallites are small enough to neglect any macroscopic effect, and not considering any interaction between amorphous and crystalline region. The discrepancies observed for some experimental points, especially at 20% RH, can be due to a slight difference in crystallinity due to plasticization induced by the water molecules. The combined model for 20% RH showed lower permeability than the experimental data, which is probably due to an underestimation of the solubility of the water as well as to the increase in diffusivity induced by the water (i.e., the mobility of the polymer chains). This combined model is able to represent the behavior of 0%RH 20%RH 50%RH 80%RH oxygen permeation through complex, filled, polymer layers at humid conditions. Conclusions The permeability of oxygen gas is expected to depend on both crystallinity and concentration of kaolin, as well as the surrounding conditions. This study has shown that the barrier capacity of oxygen in kaolinfilled PVOH film deteriorates as humidity is increased. Moreover, the kaolin hinders the proper formation of PVOH crystals and, consequently, no enhancement of the barrier coating properties was observed at RH values below 80%. At extremely high humidity (80% RH), however, the filler was able to improve the barrier properties appreciably. Lower levels of O2 permeability were measured at higher kaolin concentrations due to PVOH being solved in the water. The permeability measurements of the coatings were taken in the further development of a permeability model for filled polymeric layer described previously, which includes the ability to account also for the effect of humidity. The model showed good agreement with the experiments; it improves not only understanding of barrier performance but also how permeability is related to both filler content and RH in particular. Acknowledgments This study was performed within the multidisciplinary Industrial Graduate School VIPP (www.kau.se/en/vipp)—Values Created in Fibre-Based Processes and Products—at Karlstad University, Sweden, with the financial support of the Knowledge Foundation, Sweden (Reference Number: 20100268) and Stora Enso. The authors would also like to acknowledge the foundation Stiftelsen Disponent och Fru Christian Storjohanns Stipendiefond for financing received during secondment at DICAM, Bologna, Italy. Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. References i 1 r 1 . 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Åsa Nyflött, Çağlar Meriçer, Matteo Minelli, Ellen Moons, Lars Järnström, Magnus Lestelius, Marco Giacinti Baschetti. The influence of moisture content on the polymer structure of polyvinyl alcohol in dispersion barrier coatings and its effect on the mass transport of oxygen, Journal of Coatings Technology and Research, 2017, 1-11, DOI: 10.1007/s11998-017-9937-2