Alcohol Copolymer Films Research Articles

Biaxially stretched polyamide 6/ethylene vinyl alcohol copolymer films with improved oxygen barrier and mechanical properties

Biaxially stretched polyamide 6/ethylene vinyl alcohol copolymer films with improved oxygen barrier and mechanical properties

Structure-Property Relationship of Cellulose Nanocrystal-Polyvinyl Alcohol Thin Films for High Barrier Coating Applications.

CO2 and O2 gas permeability are paramount concerns in food packaging. Here, the permeability of cellulose nanocrystals (CNCs) and polyvinyl alcohol (PVA) coatings was explored as it relates to varied CNC content. Specifically, this work focuses on the role of PVA in rheology and barrier performance of the CNC films. Results show that shear-casted CNC films are transparent and have a high-order parameter, which is attributed to the shear-thinning behavior of the CNCs. The barrier performance of the CNC films improved because of the synergistic effect of having both alignment of CNCs and a lower free volume. The CNC-PVA films exhibited excellent barrier performance as compared to traditional engineered polymers, even much higher than high barrier ethylene-vinyl alcohol copolymer films. Furthermore, the moisture sensitivity of the films was greatly diminished with the addition of PVA. Overall, the results show applicability of CNC-PVA coating formulations for high barrier packaging applications.

Machine learning approach for predicting Fusarium culmorum and F. proliferatum growth and mycotoxin production in treatments with ethylene-vinyl alcohol copolymer films containing pure components of essential oils

Fusarium culmorum and F. proliferatum can grow and produce, respectively, zearalenone (ZEA) and fumonisins (FUM) in different points of the food chain. Application of antifungal chemicals to control these fungi and mycotoxins increases the risk of toxic residues in foods and feeds, and induces fungal resistances. In this study, a new and multidisciplinary approach based on the use of bioactive ethylene-vinyl alcohol copolymer (EVOH) films containing pure components of essential oils (EOCs) and machine learning (ML) methods is evaluated. Bioactive EVOH-EOC films were made incorporating cinnamaldehyde (CINHO), citral (CIT), isoeugenol (IEG) or linalool (LIN). Several ML methods (neural networks, random forests and extreme gradient boosted trees) and multiple linear regression (MLR) were applied and compared for modeling fungal growth and toxin production under different water activity (aw) (0.96 and 0.99) and temperature (20 and 28 °C) regimes. The effective doses to reduce fungal growth rate (GR) by 50, 90 and 100% (ED50, ED90, and ED100) of EOCs in EVOH films were in the ranges 200 to >3330, 450 to >3330, and 660 to >3330 μg/fungal culture (25 g of partly milled maize kernels in Petri dish), respectively, depending on the EOC, aw and temperature. The type of EVOH-EOC film and EOC doses significantly affected GR in both species and ZEA and FUM production. Temperature also affected GR and aw only affected GR and FUM production of F. proliferatum. EVOH-CIT was the most effective film against both species and ZEA and FUM production. Usually, when the EOC levels increased, GR and mycotoxin levels in the medium decreased although some treatments in combination with certain aw and temperature values induced ZEA production. Random forest models predicted the GR of F. culmorum and F. proliferatum and ZEA and FUM production better than neural networks or extreme gradient boosted trees. The MLR mode provided the worst performance. This is the first approach on the ML potential in the study of the impact that bioactive EVOH films containing EOCs and environmental conditions have on F. culmorum and F. proliferatum growth and on ZEA and FUM production. The results suggest that these innovative packaging systems in combination with ML methods can be promising tools in the prediction and control of the risks associated with these toxigenic fungi and mycotoxins in food.

High oxygen barrier multilayer EVOH/LDPE film/foam

ABSTRACTHigh oxygen barrier film/foam system had been developed using multilayer coextrusion technology. The film/foams contained alternating ethylene–vinyl alcohol (EVOH) copolymer film layers and low‐density polyethylene (LDPE) foam layers. To ensure good adhesion and layer integrity, the LDPE was preblended with LDPE grafted maleic anhydride. The layered structure of film/foam was characterized by scanning electron microscopy. The film/foams showed adjustable density, oxygen permeability, and mechanical properties by changing the film and foam composition. Film/foam with 10% EVOH film layer was successfully thermoformed at room temperature. The cells in the foam layer were observed to deform during the mechanical forming process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46425.

Risk management of ochratoxigenic fungi and ochratoxin A in maize grains by bioactive EVOH films containing individual components of some essential oils

Aspergillus steynii and Aspergillus tubingensis are possibly the main ochratoxin A (OTA) producing species in Aspergillus section Circumdati and section Nigri, respectively. OTA is a potent nephrotoxic, teratogenic, embryotoxic, genotoxic, neurotoxic, carcinogenic and immunosuppressive compound being cereals the first source of OTA in the diet. In this study bioactive ethylene-vinyl alcohol copolymer (EVOH) films containing cinnamaldehyde (CINHO), linalool (LIN), isoeugenol (IEG) or citral (CIT) which are major components of some plant essential oils (EOs) were produced and tested against A. steynii and A. tubingensis growth and OTA production in partly milled maize grains. Due to the favourable safety profile, these bioactive compounds are considered in the category “GRAS”. The study was carried out under different water activity (0.96 and 0.99 aw), and temperature (24 and 32 °C) conditions. ANOVA showed that class of film, fungal species, aw and temperature and their interactions significantly affected growth rates (GR), ED50 and ED90 and the doses for total fungal growth inhibition and OTA production. The most effective EVOH films against both species were those containing CINHO. ED50, ED90 and doses for total growth and OTA inhibition were 165–405, 297–614, 333–666 μg of EVOH-CINHO/plate (25 g of maize grains), respectively, depending on environmental conditions. The least efficient were EVOH-LIN films. ED50, ED90 and doses for total growth and OTA inhibition were 2800–>3330, >3330 and >3330 μg of EVOH-LIN/plate (25 g of maize grains), respectively. The effectiveness of the bioactive films increased with increasing doses. Overall, A. tubingensis was less sensitive to treatments than A. steynii. Depending on the species, aw and temperature affected GR and OTA production in a different way. In A. steynii cultures, optimal growth occurred at 0.96 aw and 32 °C while optimal OTA production happened at 0.99 aw and 32 °C. In A. tubingensis cultures optimal growth happened at 0.99 aw and 32 °C, although the best conditions for OTA production were 0.99 aw and 24 °C. Thus, these species can be very competitive in warm climates and storage conditions. The EVOH-CINHO films followed by EVOH-IEG and EVOH-CIT films, designed in this study and applied in vapour phase, can be potent antifungal agents against A. steynii and A. tubingensis and strong inhibitors of OTA biosynthesis in maize grains at very low doses. This is the first study on the impact that interacting environmental conditions and bioactive films containing individual components of EOs have on the growth of these ochratoxigenic fungi and on OTA production in maize grains.

Comparative characteristics of TEMPO-oxidized cellulose nanofibers and resulting nanopapers from bamboo, softwood, and hardwood pulps

Bamboo, softwood, and hardwood pulp fibers were used as starting materials to prepare TEMPO-oxidized nanofibrillated cellulose (TO-NFC) dispersions. The resulting TO-NFC dispersions were then used to fabricate cellulose nanopapers and to coat poly(lactic acid) (PLA) films. The chemical and morphological characteristics of the dispersions together with the physical properties of the resultant nanopaper and PLA films were systematically compared. The maximum degree of oxidation was achieved for the bamboo pulp fiber. Transmission electron microscopy micrographs revealed that the oxidized pulp fibers were successfully disintegrated into cellulose nanofibrils with an average width of 5–6 nm. However, bamboo-derived TO-NFC was more densely entangled and crimped, with a heterogeneous distribution in width. It was further revealed that morphologies of the obtained TO-NFC may arise from the organizational structure of microfibrils in the cellulose fibers rather than the presence of hemicelluloses or the pulping process. The PLA films coated with a thin layer of TO-NFC from the bamboo pulp exhibited the highest oxygen-barrier property, which was even slightly higher than commercial ethylene–vinyl alcohol copolymer film, known for its high oxygen-barrier functionality.

Impact of bioactive packaging systems based on EVOH films and essential oils in the control of aflatoxigenic fungi and aflatoxin production in maize

Aspergillus flavus and A. parasiticus are the most common fungal species associated with aflatoxin (AF) contamination of cereals, especially maize, and other agricultural commodities. AFB1, the most frequent and toxic metabolite, is a powerful hepatotoxic, teratogenic and mutagenic compound. Effective strategies to control these fungal species and AFs in food and feed are required. Active packaging film containing essential oils (EO) is one of the most innovative food packaging concepts. In this study, ethylene-vinyl alcohol (EVOH) copolymer films incorporating EO from Origanum vulgare (ORE), Cinnamomum zeylanicum (CIN) or their major active constituents, carvacrol (CAR) and cinnamaldehyde (CINHO), respectively, were developed and assayed to control growth of A. flavus and A. parasiticus and AF production in maize grains under different aw and temperature regimens. EO doses assayed in cultures were in the range 0.25–4.0mg/Petri dish. The factors aw, temperature, type of EVOH-EO film and fungal species significantly influenced the ED50 values of all assayed films. Growth rate (GR) of both species was usually higher at 0.99 than at 0.96 aw and at 37°C than at 25°C. However, the contrary was found with regard to AF production. The order of efficacy of EVOH-EO films to control growth of both species and AF production was EVOH-CINHO>EVOH-CAR>EVOH-ORE>EVOH-CIN. The effective dose (ED50) (mg EO/plate) for EVOH-CINHO and EVOH-CIN films against A. flavus were in the ranges of 0.125 and 2.475–3.500 and against A. parasiticus in the ranges of 0.121–0.133 and 2.275–3.625, respectively. Under the assayed conditions, the ED90 for EVOH-CINHO film were 0.22–0.23mg/plate for both species. It was the most effective bioactive film to control fungal growth (vapour phase) and AF production, regardless of aw and temperature. This is the first study about the impact that interacting environmental conditions and bioactive EVOH-CINHO, EVOH-ORE, EVOH-CIN EVOH-CAR films have on the growth of aflatoxigenic fungi and on AF production in maize grains.

Effects of Sorbic Acid-Chitosan Microcapsules as Antimicrobial Agent on the Properties of Ethylene Vinyl Alcohol Copolymer Film for Food Packaging.

This paper discusses the possibility of using sorbic acid-chitosan microcapsules (S-MPs) as an antibacterial component of active ethylene vinyl alcohol copolymer (EVOH) film. S-MPs with a diameter of approximately 1 to 4 μm showed a sorbic acid loading capacity of 46.5%. Addition of S-MPs (3%, w/w) increased the tensile strength, haze, oxygen, and water vapor barrier properties, as well as reduced the elongations at break and transmittance of S-MPs-EVOH (S-MP-EVOH) film. Antibacterial tests showed that the inhibitory capacity of S-MP-EVOH film against Salmonella Enteritidis and Escherichia coli was higher than that against Listeria monocytogenes. Moreover, the antibacterial effect of sorbic acid-EVOH (S-EVOH) film was stronger than that of S-MP-EVOH film. However, S-MP-EVOH film demonstrated a longer effective time than S-EVOH film. Using the total viable counts and total volatile base nitrogen as the judgment standard, S-MP-EVOH/polyethylene terephthalate (PET) composite film could extend the shelf life of fish fillets by 4 d at 4 °C, compared with EVOH/PET film. For this reason, S-MP could be a potential antibacterial component of active films.

Active Packaging Films from Ethylene Vinyl Alcohol Copolymer and Clove Essential Oil as Shelf Life Extenders forGrass CarpSlice

Active packaging provides a way to prevent the food putrefaction effectively. Various studies provide information on the actual preservation effect of active packaging or the migration of active agents from active films into various food stimulants separately. However, there is little related data available regarding the combined analysis of release and preservation effect. In this work, we examined the properties of active food packaging films successfully produced by extrusion of ethylene vinyl alcohol copolymer (EVOH) films with clove essential oil (C). The characterization of mechanical, thermal and barrier properties of the packaging polymers film showed that the addition of clove essential oil did not decrease their properties and C as plasticizer improved process fluidity of EVOH resin. The release of C from film to various food stimulants was measured by using HPLC, and Fickian diffusion models were used to fit the data with appropriate equation. The effects of E/C (ethylene vinyl alcohol copolymer/clove essential oil) films on quality assessment of Grass Carp slice based on sensory analysis and biochemical indices during refrigerated storage (4 ± 1°C) were examined over the period of 10 days. Total volatile basic nitrogen (TVB-N), total viable counts, pH, TBA, water holding capacity (WHC) and texture properties were evaluated. The results indicated that the active film containing 3% clove essential oil had different release parameters in four food stimulants and it could effectively maintain the fish freshness and extend the shelf life to 7–8 days during cold storage compared with control group, which was only 4 days. Copyright © 2016 John Wiley & Sons, Ltd.

Physical, mechanical, and antimicrobial properties of ethylene vinyl alcohol copolymer/chitosan/nano-ZnO (ECNZn) nanocomposite films incorporating glycerol plasticizer

In this study the ethylene vinyl alcohol copolymer (EVOH) and chitosan polymers mixture film containing nano zinc oxide (nano-ZnO) and glycerol was developed for food packaging. Physical, mechanical and antimicrobial properties of the film matrix were evaluated at different ratios of the biodegradable polymers (0:100, 25:75, 50:50, 75:25, 100:0) which contain nano-ZnO and incorporate with glycerol as the plasticizer. Film topography and cross-sections were evaluated by FE-SEM and AFM examinations. To assess characterization of the nanocomposites structure and network chemistry, FTIR spectroscopy was considered. The results indicate that EVOH improved barrier properties, transparency and mechanical properties. The antimicrobial properties were improved by adding chitosan. With adding glycerol decreases in barrier properties and increases in percentage of elongation at break (eb) were observed. Adding nano-ZnO improved barrier, mechanical and antimicrobial properties and significantly reduced the adverse effects of glycerol. Taken together, these data reveal that the new nanocomposite provides the better properties and the less adverse effects of plasticizer on matrix film.

Antioxidant and antimicrobial properties of ethylene vinyl alcohol copolymer films based on the release of oregano essential oil and green tea extract components

Polymer films with antioxidant and antimicrobial properties were manufactured for the active packaging of food products. Green tea extract (GTE) and oregano essential oil (OEO) were incorporated in an ethylene–vinyl alcohol copolymer (EVOH). Release studies of the main active components of the films into three food simulants, 3% acetic acid, 10% ethanol and 50% ethanol, were conducted at 4°C and 23°C. The total antioxidant activity at equilibrium was measured in the food simulants and the antimicrobial capacity of the films was tested in vitro against Listeria monocytogenes, Escherichia coli and Penicillium expansum. The results suggest that the release kinetics depend on the affinity between the active agents and the food simulants. In general, the fastest diffusion was obtained when films were exposed to 50% ethanol and that effect was concurrent with greater antioxidant efficiencies. The films also showed microbial growth inhibition in liquid media and in vapour phases, demonstrating that the developed films show strong potential for development as active food packaging films.

Nano-Ag Doping Induced Changes in the Optical Behavior and Thermal Stability of Acrylic Acid-Grafted Poly Vinyl Alcohol Copolymer Films

Metal–polymer nanocomposites have been prepared from an aqueous solution of polyvinyl alcohol/acrylic acid (PVA/AAc) and silver nitrate (AgNO3). The functionalized PVA/AAc was copolymerized and cross-linked using electron beam irradiation. The prepared nanocomposites were characterized by FTIR, TEM and TGA. The average grain size is in the range of 15–44 nm, depending on Ag concentration. The thermal stability was found to increase and the optical band gap decreased with the increase of dopant concentration. The real and imaginary parts of the dielectric constant, optical conductivity, volume energy loss (VELF) and surface energy loss (SELF) of the films were also determined.

Development and Characterization of Silver-Based Antimicrobial Ethylene–Vinyl Alcohol Copolymer (EVOH) Films for Food-Packaging Applications

The use of silver as an antimicrobial in the food area has raised wide interest in recent years. In the present work, 0.001-10 wt % silver ions was satisfactorily incorporated into an ethylene-vinyl alcohol (EVOH) copolymer matrix by a solvent casting technique. The antibacterial efficacy of the composite was evaluated under laboratory conditions and in contact with some foods. The ionic compound did not affect the crystallinity or the water-induced plasticization of the materials and was homogeneously distributed across the surface and thickness of the films. When immersed in water, sorption-induced release of 50-100% of the silver ions took place in <30 min. In the bacterial minimal growth medium M9, the minimal inhibitory concentration (MIC) of the film was in the range of 0.01-0.1 ppm. High protein content food samples displayed low susceptibility to the films (<1 log reduction in any case), whereas low protein content food samples exhibited no detectable bacterial counts for films with 1 and 10 wt % silver and about 2 log reduction for films with 0.1 wt % silver. These results represent a step forward in the understanding of silver antimicrobial efficacy and its possible application in the food-packaging industry, most likely as food coatings.

Reducing Oxidation of Foods Through Antioxidant Active Packaging Based on Ethyl Vinyl Alcohol and Natural Flavonoids

The development of antioxidant active packaging systems is attracting considerable attention as one of the preferred emerging technologies for reducing the incidence of lipid peroxidation. This work presents the use of ethylene vinyl alcohol copolymer films containing two natural flavonoids, catechin and quercetin, to reduce the oxidation of food. In a series of experiments, these materials showed their ability to reduce the presence of hydroxyl radicals in the package headspace. Packaging fried peanuts in bags manufactured with these active films resulted in a large reduction in the presence of hexanal, a compound produced during peroxidation of the unsaturated fat in peanuts. The results indicated that the materials actively reduced the presence of radical oxidative species although the antioxidants are not released into the food. On exposing sunflower oil to the films, the peroxide values obtained showed that the films actively protected the oil; because of the higher solubility of quercetin in this food product as well as the higher antioxidant capacity, the samples containing this flavonoid were more efficient.Industrial relevance: Active packaging is receiving considerable attention as an emerging technology that can be used to improve the quality and the stability of food, reducing the direct addition of chemicals and the need for changes in formulation. The results of this study show that it is possible to reduce food oxidation without adding antioxidants to the food. The films obtained can be used to protect any type of food, including dry or fatty products. Copyright © 2012 John Wiley &amp; Sons, Ltd.

Development of New Antioxidant Active Packaging Films Based on Ethylene Vinyl Alcohol Copolymer (EVOH) and Green Tea Extract

Ethylene vinyl alcohol copolymer (EVOH) films containing green tea extract were successfully produced by extrusion. The films were brown and translucent, and the addition of the extract increased the water and oxygen barrier at low relative humidity but increased the water sensitivity, the glass transition temperature, and the crystallinity of the films and improved their thermal resistance. An analysis by HPLC revealed that the antioxidant components of the extract suffered partial degradation during extrusion, reducing the content of catechin gallates and increasing the concentration of free gallic acid. Exposure of the films to various food simulants showed that the liquid simulants increased their capacity to reduce DPPH(•) and ABTS(•+) radicals. The release of green tea extract components into the simulant monitored by HPLC showed that all compounds present in the green tea extract were partially released, although the extent and kinetics of release were dependent on the type of food. In aqueous food simulants, gallic acid was the main antioxidant component released with partition coefficient values ca. 200. In 95% ethanol (fatty food simulant) the K value for gallic acid decreased to 8 and there was a substantial contribution of catechins (K in the 1000 range) to a greatly increased antioxidant efficiency. Kinetically, gallic acid was released more quickly than catechins, owing to its faster diffusivity in the polymer matrix as a consequence of its smaller molecular size, although the most relevant effect is the plasticization of the matrix by alcohol, increasing the diffusion coefficient >10-fold. Therefore, the materials here developed with the combination of antioxidant substances that constitute the green tea extract could be used in the design of antioxidant active packaging for all type of foods, from aqueous to fatty products, the compounds responsible for the protection being those with the higher compatibility with the packaged product.

Preliminary in vivo study of apatite and laminin‐apatite composite layers on polymeric percutaneous implants

A polymeric material coated with a hydroxyapatite (HA) layer would be useful as a flexible percutaneous device with good biocompatibility and resistance to bacterial infection. We have recently developed a simple, safe, and mild coating process to form an HA layer on the surfaces of polymeric materials. In this study, our coating process was applied to an ethylene-vinyl alcohol copolymer film. The resulting HA-coated film was percutaneously implanted in the scalp of a rat to examine the stability and biocompatibility of the HA layer. From the results of histological analysis, the HA layer remained undissolved on the film surface under the skin tissue even 3 days after implantation. Owing to the good biocompatibility of HA, the HA-coated film suppressed a host's foreign-body response and integrated with the surrounding skin tissue for as long as 14 days, in a similar fashion to a conventional percutaneous device composed of ceramic HA. Immobilization of a cell adhesion protein, laminin, into the HA layer was found to improve the adhesion strength between the film and the surrounding skin tissue without compromising good biocompatibility of HA. Our coating process to form HA and laminin-HA composite layers would be useful in fabricating polymeric percutaneous devices with a reduced risk of bacterial infection, although further in vivo studies are required.

Food applications of active packaging EVOH films containing cyclodextrins for the preferential scavenging of undesirable compounds

Novel ethylene-vinyl alcohol copolymer (EVOH) films containing beta-cyclodextrins (βCD) with potential application in active food packaging have been tested as materials for the preferential retention of undesired food components. The films were immersed on pasteurized milk and UHT milk and stored at 4 and 23 °C, respectively. The films containing βCD presented a significant reduction in cholesterol concentration, achieving a 23% reduction in UHT milk exposed to EVOH films containing 30% βCD. Despite the immobilization of the βCD and the large molecular size of cholesterol, 15% of the βCD molecules added to the films were involved in the formation of βCD/cholesterol inclusion complexes. In another set of experiments, the films were used to reduce the presence of aldehydes (substances which develop as a result of oxidative processes) in packaged fried peanuts. The films containing βCD brought a significant reduction in hexanal, reaching a 50% decrease over short periods (1–5 weeks). At longer storage times (10 weeks) the retention capacity of the developed films was exhausted and no differences were observed between the samples.

Improving the Antioxidant Protection of Packaged Food by Incorporating Natural Flavonoids into Ethylene−Vinyl Alcohol Copolymer (EVOH) Films

Ethylene-vinyl alcohol copolymer (EVOH) films containing catechin or quercetin as antioxidant agents were successfully produced by extrusion. The addition of these bioactive compounds did not modify greatly their water and oxygen permeabilities, Tg, or crystallinity but improved their thermal resistance. Exposure of the films to different food simulants showed that both compounds were released, although the extent and kinetics of release were dependent on the type of food. In aqueous and alcoholic food simulants their release was greater in the case of the catechin-containing samples. Exposure of the films to isooctane and ethanol 95% (fatty food simulants) provided controversial results; no release was observed in isooctane, whereas both bioactive compounds were extracted by ethanol due to their high solubility in alcohol and the plasticizing effect of ethanol on the polymer. Packaging applications of these films can improve food stability and provide a method for adding such bioactive compounds.

Surface Chemical Analysis of Plasma‐Deposited Copolymer Films Prepared from Feed Gas Mixtures of Ethylene or Styrene with Allyl Alcohol

AbstractPlasma deposited styrene/allyl alcohol and ethylene/allyl alcohol copolymer films were prepared and characterized using XPS, NEXAFS and ToF‐SIMS. The relative partial flow rates of the co‐monomers are used as deposition process parameters to vary and all other process parameters were constrained to conditions optimized for retention of functional groups. By doing this it is possible to control certain chemical properties of the copolymer films such as unsaturation, oxygen and hydroxyl group relative surface contents. The aging behavior of the plasma copolymer films on air was studied, too. Non‐linear variations of relative oxygen contents, contents of COR species and contents of carbonyl species are obtained vs. variation of feed gas composition for both monomer combinations. The chemical character of the plasma copolymer films varies between the limits given by the respective plasma homopolymers. The observed non‐linear correlations are discussed in terms of approaches developed for classic radical copolymerization. The aging behavior of the different plasma copolymers films depends on the feed gas composition. Principally these aging phenomena known from plasma polymer aging studies of that respective monomer which dominates the character of the plasma copolymer are observed.magnified image

Static ToF-SIMS analysis of plasma chemically deposited ethylene/allyl alcohol co-polymer films

A plasma co-polymerization of ethylene as a “chain extending” monomer and allyl alcohol as a carrier monomer for hydroxyl groups was studied. The composition of the feed gas was systematically varied and the plasma co-polymers were analyzed in terms of their relative concentrations of OH functional groups by static Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) immediately after their preparation without any air contact, i.e., under so called “in situ” conditions. The relative OH group concentration involved in the –CH 2–OH groups was derived from the normalized yields of the CH 3O + secondary fragment ion. The density of functional groups in the plasma co-polymers was found to vary non-linearly with respect to the mole percentage of the monomers in the feed gas. Co-polymerization phenomena, i.e. chemical interactions and recombination reactions taking place between monomer molecules in the plasma and/or during the deposition process, become evident in ToF-SIMS spectra.