Biodegradable polymer blends and composites: An overview

Biodegradable polymers belong to a family of polymer materials that found applications ranged from medical applications including tissue engineering, wound management, drugs delivery, and orthopedic devices, to packaging and films applications. For broadening their potential applications, biodegradable polymers are modified utilizing several methods such as blending and composites forming, which lead to new materials with unique properties including high performance, low cost, and good processability. This paper reviews the recent information about the morphology of blends consisting of both biodegradable and non-biodegradable polymers and associated mechanical, rheological, and thermal properties of these systems as well as their degradation behavior. In addition, the mechanical performance of composites based on biodegradable polymers is described.     

Development of Passive and Active Barrier Coatings on the Basis of Inorganic–Organic Polymers

Summary. With a new kind of barrier coating material, namely inorganic–organic polymers, it is possible to obtain excellent barrier properties against oxygen, water vapor, and flavor permeation. These hybrid polymers can be synthesized by the sol–gel technique. If extremely low permeation values are needed, the combination of hybrid polymer coatings with thin inorganic oxidic layers (SiO_x, AlO_x) is very effective and leads to permeation values for oxygen and water vapor below 10⁻³ cm³/m² · d · bar or g/m² · d. These passive barrier layers can be further improved by the combination with active oxygen barrier layers which have been developed for the food packaging industry. This approach makes these multilayer laminates promising candidates for special applications in the food packaging industry as well as for sophisticated applications in technical areas: the encapsulation of sensitive organic devices like solar cells, organic light emitting diodes, or polymer electronic systems.     

Injection stretch blow moulding process of reactive extruded recycled PET and virgin PET blends

Reactive extruded recycled PET (RER-PET) was blended with virgin PET in order to find optimum composition for producing bottles using injection stretch blow moulding (ISBM) process. Two variables were investigated namely, RER-PET concentration in the blend with virgin PET and RER-PET intrinsic viscosity, [η]. The variability of [η] was facilitated by changing PMDA chain extender concentration in the production of RER-PET. Different molecular, mechanical, barrier and optical tests such as infrared, burst pressure, top load strength, drop impact, environmental stress cracking, liquid permeation, gas permeation, and clarity were conducted. The aim was to evaluate the properties of the bottles in response to different blends compositions. Bottles made from RER-PET and virgin PET blends showed similar and better mechanical and barrier properties at certain compositions to those made from Virgin PET. The effects of RER-PET molecular properties such as intrinsic viscosity, chain orientation and conformation on bottles mechanical, barrier and optical properties are detailed.     

An overview of polylactides as packaging materials

Polylactide polymers have gained enormous attention as a replacement for conventional synthetic packaging materials in the last decade. By being truly biodegradable, derived from renewable resources and by providing consumers with extra end-use benefits such as avoiding paying the "green tax" in Germany or meeting environmental regulations in Japan, polylactides (PLAs) are a growing alternative as a packaging material for demanding markets. The aim of this paper is to review the production techniques for PLAs, summarize the main properties of PLA and to delineate the main advantages and disadvantages of PLA as a polymeric packaging material. PLA films have better ultraviolet light barrier properties than low density polyethylene (LDPE), but they are slightly worse than those of cellophane, polystyrene (PS) and poly(ethylene terephthalate) (PET). PLA films have mechanical properties comparable to those of PET and better than those of PS. PLA also has lower melting and glass transition temperatures than PET and PS. The glass transition temperature of PLA changes with time. Humidity between 10 and 95% and storage temperatures of 5 to 40 degrees C do not have an effect on the transition temperature of PLA, which can be explained by its low water sorption values (i.e. <100 ppm at Aw = 1). PLA seals well at temperatures below the melting temperature but an appreciable shrinking of the films has been noted when the material is sealed near its melting temperature. Solubility parameter predictions indicate that PLA will interact with nitrogen compounds, anhydrides and some alcohols and that it will not interact with aromatic hydrocarbons, ketones, esters, sulfur compounds or water. The CO2, O2 and water permeability coefficients of PLA are lower than those of PS and higher than those of PET. Its barrier to ethyl acetate and D-limonene is comparable to PET. The amount of lactic acid and its derivatives that migrate to food simulant solutions from PLA is much lower than any of the current average dietary lactic acid intake values allowed by several governmental agencies. Thus, PLA is safe for use in fabricating articles for contact with food.     

Evaluation of the transport properties of Poly(3-hydroxybutyrate) and its 3-hydroxyvalerate copolymers for packaging applications

Poly(3-hydroxybutyrate) (PHB) and ist 3-hydroxyvalerate containing copolymers form a family of fully biodegradable polyesters with many potential applications. In this work, the results obtained in our laboratory concerning carbon dioxide, water and organic solvent transport through PHB and three low 3-hydroxyvalerate copolymers are reviewed. Comparison established between the former results and some data taken from the literature, have revealed that PHB and the above mentioned copolymers show transport properties similar to other common thermoplastics such as PVC and PET, particularly in the case of carbon dioxide and water. Consequently, PHB and copolymers can be catalogued as good barrier materials against these penetrants. On the other hand, these biopolymers show a low barrier character against organic compound permeation. All these features conform a good balance of physicochemical properties for these polyhydroxyalkanoates, which may take them suitable for several applications, including its use in biodegradable packaging materials.     

Fracture evaluation of plasticized polylactic acid / poly (3-HYDROXYBUTYRATE) blends for commodities replacement in packaging applications

Nowadays, scientific and technological efforts are being carried out to diminish serious ecological problems caused by indiscriminate use of non-biocompostable polymers in the packaging industry. In this sense, novel biodegradable blends of different composition based on poly(lactic acid) (PLA), poly(3-hydroxybutyrate) (PHB) and tributyrin (TB) are developed and here proposed as an eco-friendly alternative. Materials are characterized by fracture experiments under quasi-static and biaxial impact loading. Fracture behavior is analyzed together with thermal, tensile and water permeation properties to evaluate their potential in-service performance. TB_PLA/PHB blends with 15 wt% TB exhibit better permeation and fracture toughness than currently used bio-based polymers, being in the range of polyethylene properties. Results highlight the potential of these new blends broadening the current application field of PLA.     

Giant persistent antimicrobial and biocompatible polyester fabrics for anti-mold food packaging

Polyethylene terephthalate (PET) fibers have been the most popular fabrics owing to their superior performances. However, PET fabrics generally wear uncomfortably because of their poor sweat absorbing ability, electrostatic charge accumulation, and unfavorable microorganisms. To endow PET fabrics with perdurable antimicrobial and antistatic properties by conventional methods is unachievable owing to the absence of reactive groups. Herein, we developed a one-step facile strategy for preparing antimicrobial PET fabrics via photochemical reaction using benzophenone terminated Gemini quaternary ammonium salt (GQAS) and Gemini betaine as the antimicrobial finishing reagents. The antimicrobial rate of GQAS finished PET fabrics and GQAS/Gemini betaine finished PET fabrics were greater than 91% against both the gram-negative Escherichia coli and the gram-positive Staphylococcus aureus after 50 laundering cycles, which were significantly better than usual antimicrobial fabrics. In addition, the antimicrobial PET fabrics showed prominently enhanced hydrophilic, antistatic and long-lasting antimicrobial properties, as well as negligible toxicity. Most importantly, this work proposes a universal and efficient strategy for the development of permanent antimicrobial and antistatic synthetic polymers without compromising their superiority those have great potential for industrial and healthcare applications, including but not limited to food packaging, clothes and medical appliances to prevent infectious diseases and mildew.     

Modified whey protein coatings for improved gas barrier properties of biodegradable films

As a result of environmental concern, there is an increasing interest in the development of biodegradable polymers for packaging with suitable properties, as an alternative to the synthetic petroleum‐based polymers. However, such biodegradable polymers are prevented for use in wide industrial and commercial packaging because of their limited gas and vapor barrier properties. This obstacle urges innovative strategies to achieve enhanced gas barrier properties using “bio‐layering” technologies. Whey protein isolate (WPI), a by‐product of the cheese industry, has quite promising properties for packaging purposes. It possesses good oxygen, aroma, and oil barrier properties; however, its permeability to water vapor is high. In this study, several WPI coatings were obtained, adding polyvinyl alcohol and pectin to improve the coated film properties; in addition, nanoclays were used to improve water vapor barrier properties. Comparison of neat poly (lactic acid) film versus poly (lactic acid) coated with WPI presented advantage of the later: improvement of about 90% in the oxygen barrier properties and about 27% in the water vapor barrier properties. Copyright © 2016 John Wiley & Sons, Ltd.     

Poly Lactic Acid (PLA) Nanocomposites: Effect of Inorganic Nanoparticles Reinforcement on Its Performance and Food Packaging Applications

Poly lactic acid (PLA) is a compostable, as well as recyclable, sustainable, versatile and environmentally friendly alternative, because the monomer of PLA-lactide (LA) is extracted from natural sources. PLA’s techno-functional properties are fairly similar to fossil-based polymers; however, in pristine state, its brittleness and delicacy during processing pose challenges to its potential exploitation in diverse food packaging applications. PLA is, therefore, re-engineered to improve its thermal, rheological, barrier and mechanical properties through nanoparticle (NP) reinforcement. This review summarises the studies on PLA-based nanocomposites (PLA NCs) developed by reinforcing inorganic metal/metallic oxide, graphite and silica-based nanoparticles (NPs) that exhibit remarkable improvement in terms of storage modulus, tensile strength, crystallinity, glass transition temperature (Tg) value, antimicrobial property and a decrease in water vapour and oxygen permeability when compared with the pristine PLA films. This review has also discussed the regulations around the use of metal oxide-based NPs in food packaging, PLA NC biodegradability and their applications in food systems. The industrial acceptance of NCs shows highly promising perspectives for the replacement of traditional petrochemical-based polymers currently being used for food packaging.     

Synthesis of bio‐based poly(ethylene 2,5‐furandicarboxylate) copolyesters: Higher glass transition temperature,better transparency,and good barrier properties

The bio‐based polyester, poly(ethylene 2,5‐furandicarboxylate) (PEF), was modified by 2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol (CBDO) via copolymerization and a series of copolyesters poly(ethylene‐co‐2,2,4,4‐tetramethyl‐1,3‐cyclobutanediol 2,5‐furandicarboxylate)s (PETFs) were prepared. After their chemical structures and sequence distribution were confirmed by nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), their thermal, mechanical, and gas barrier properties were investigated in detail. Results showed that when the content of CBDO unit in the copolyesters was increased up to 10 mol%, the completely amorphous copolyesters with good transparency could be obtained. In addition, with the increasing content of CBDO units in the copolyesters, the glass transition temperature was increased from 88.9 °C for PET to 94.3 °C for PETF‐23 and the tensile modulus was increased from 3000 MPa for PEF to 3500 MPa for PETF‐23. The barrier properties study demonstrated that although the introduction of CBDO units would increase the O₂ and CO₂ permeability of PEF slightly, PECF‐10 still showed better or similar barrier properties compared with those of PEN and PEI. In one word, the modified PEF copolyesters exhibited better mechanical properties, higher glass transition temperature, good barrier properties, and better clarity. They have great potential to be the bio‐based alternative to the popular petroleum‐based poly(ethylene terephthalate) (PET) when used as the beverage packaging materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3298–3307     

Recent progress in microporous polymers from thermally rearranged polymers and polymers of intrinsic microporosity for membrane gas separation: Pushing performance limits and revisiting trade-off lines

Polymers are promising materials for gas separation membranes. However, the trade-off relationship between gas permeability and selectivity remains an obstacle for achieving polymer membranes that exhibit high gas permeation with desirable separation efficiency. Improving polymer microporosity is of interest in gas separation membranes to enhance gas transport behavior. Polymer modifications by (a) incorporating intrinsically microporous units and/or (b) increasing chain rigidity can enhance microporosity in conventional polymer membrane materials such as polyimides. These strategies are adopted for new classes of microporous polymers, thermally rearranged (TR) polymers, and polymers with intrinsic microporosity (PIMs), to maximize gas transport properties. Their outstanding gas separation performances have redefined the traditional trade-off lines. This review aims to explore the advances in microporous polymers for gas separation applications. The approaches on TR polymers and PIMs to enhance their microporosity are listed, and their developments are evaluated in the context of revisiting performance limits for industrially relevant gas separation applications.     

Preparation and characterization of nonfouling polymer brushes on poly(ethylene terephthalate) film surfaces

In this study, a surface grafting of nonfouling poly(ethylene glycol) methyl ether acrylate (PEGMA) on poly(ethylene terephthalate) (PET) was carried out via surface-initiated atom-transfer radical polymerization (SI-ATRP) to improve hemocompatibility of polymer based biomaterials. To do this, the coupling agent with hydroxyl groups for the ATRP initiator was first anchored on the surface of PET films using photochemical method, and then these hydroxyl groups were esterified by bromoisobutyryl bromide, from which PET with various main chain lengths of PEGMA was prepared. The structures and properties of modified PET surfaces were investigated using water contact angle (WAC), ATR-FTIR, X-ray photoelectron spectroscopy (XPS) and Atomic force microscopy (AFM). The molecular weights of the free polymer from solution were determined by gel permeation chromatography (GPC). These results indicated that grafting of PEGMA on PET film is a simple way to change its surface properties. The protein adsorption resistance on the surfaces of PET was primarily evaluated by an enzyme-linked immunosorbent assay (ELISA). The result demonstrated that the protein adsorption could be well suppressed by poly(PEGMA) brush structure on the surface of PET. This work provides a new approach for polymers to enhance their biocompatibility.     

Surface modification of sepiolite in aqueous gels by using methoxysilanes and its impact on the nanofiber dispersion ability

Surface modification reactions on needle-like sepiolite using alkyl and functional silanes have been carried out in the form of aqueous gels. In contrast with modifications in organic solvents, reactions in water make it possible to modify the surface of almost-individual sepiolite fibers and produce either a continuous coating or a nanotexturization of the sepiolite fiber surface, depending on the reaction conditions. This clean procedure substitutes advantageously organic solvent surface modifications and allows the tuning of surface properties such as specific surface area, wetting behavior, and chemical functionalization. A consequence of such tuning is, for example, the excellent dispersion of modified sepiolite nanofibers in a great variety of polymers by routine compounding and processing techniques.     

Effect of small amounts of poly(lactic acid) on the recycling of poly(ethylene terephthalate) bottles

Poly(ethylene terephthalate) (PET) is one of the most used commodity polymers, especially for food and beverage applications, and its recycling is of great importance because of the possible use in the textile and construction industries. On the other hand, the interest in biodegradable polymers has led, in recent years, to the use of materials such as poly(lactic acid) (PLA) also in the food and beverage industry. The presence of small amounts of PLA in the PET waste can significantly affect the post-consumer recycling process. In this work, the effect of the presence of small amounts of PLA on the recycling of PET bottles is investigated by rheological, mechanical, morphological and thermogravimetric analysis. The results indicate that this presence can significantly affect the rheological properties under non-isothermal elongational flow, while the mechanical properties were considerably affected only in some circumstances and the thermal stability was not significantly modified.     

Assessing the thermoformability of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(acid lactic) blends compatibilized with diisocyanates

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a renewable alternative to conventional barrier packaging polymers due to its thermoplastic properties, biodegradability and gas barrier performance but its potential industrial applications are limited by its high price and difficult processability. A thorough study concerning the thermoforming ability of PHBV, and blends with poly(lactic acid) (PLA) incorporating three different diisocyanates as compatibilizers (hexamethylene diisocyanate, poly(hexamethylene) diisocyanate and 1,4-phenylene diisocyanate) is herein presented after component melt blending. A straightforward universal qualitative method is proposed to assess the thermoformability, based on a visual inspection of a thermoformed specimen and the ability to reproduce the mold shape, and the thermoforming window of the material. The results reveal a significant improvement in the thermoforming capacity and a widening of the thermoforming windows as the correct amounts of diisocyanates are incorporated. The barrier properties and the biodisintegrability of the blends was also studied, confirming a predictable slight decrease of the barrier performance when PLA is added, but without negatively affecting the disintegrability under composting conditions with respect to pristine PHBV.     

Electrochemical sensors and biosensors based on redox polymer/carbon nanotube modified electrodes: A review

The aim of this review is to present the contributions to the development of electrochemical sensors and biosensors based on polyphenazine or polytriphenylmethane redox polymers together with carbon nanotubes (CNT) during recent years. Phenazine polymers have been widely used in analytical applications due to their inherent charge transport properties and electrocatalytic effects. At the same time, since the first report on a CNT-based sensor, their application in the electroanalytical chemistry field has demonstrated that the unique structure and properties of CNT are ideal for the design of electrochemical (bio)sensors. We describe here that the specific combination of phenazine/triphenylmethane polymers with CNT leads to an improved performance of the resulting sensing devices, because of their complementary electrical, electrochemical and mechanical properties, and also due to synergistic effects. The preparation of polymer/CNT modified electrodes will be presented together with their electrochemical and surface characterization, with emphasis on the contribution of each component on the overall properties of the modified electrodes. Their importance in analytical chemistry is demonstrated by the numerous applications based on polymer/CNT-driven electrocatalytic effects, and their analytical performance as (bio) sensors is discussed.     

Modern mass spectrometry in the characterization and degradation of biodegradable polymers

In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization time of flight) and ESI MS (electrospray mass spectrometry) for the determination of the structural architecture of biodegradable macromolecules, including their topology, composition, chemical structure of the end groups have been reported. However, MS methodologies have been recently applied to evaluate the biodegradation of polymeric materials. ESI MS represents the most useful technique for characterizing water-soluble polymers possessing different end group structures, with the advantage of being easily interfaced with solution-based separation techniques such as high-performance liquid chromatography (HPLC).     

Comparison of nano- and microfibrillated cellulose films

Nanocellulose is an interesting building block for functional materials and has gained considerable interest due to its mechanical robustness, large surface area and biodegradability. It can be formed into various structures such as solids, films and gels such as hydrogels and aerogels and combined with polymers or other materials to form composites. Mechanical, optical and barrier properties of nanofibrillated cellulose (NFC) and microfibrillated cellulose (MFC) films were studied in order to understand their potential for packaging and functional printing applications. Impact of raw material choice and nanocellulose production process on these properties was evaluated. MFC and NFC were produced following two different routes. NFC was produced using a chemical pretreatment followed by a high pressure homogenization, whereas MFC was produced using a mechanical treatment only. TEMPO-mediated oxidation followed by one step of high pressure (2,000 bar) homogenization seems to produce a similar type of NFC from both hardwood and softwood. NFC films showed superior mechanical and optical properties compared with MFC films; however, MFC films demonstrated better barrier properties against oxygen and water vapor. Both the MFC and NFC films were excellent barriers against mineral oil used in ordinary printing inks and dichlorobenzene, a common solvent used in functional printing inks. Barrier properties against vegetable oil were also found to be exceptionally good for both the NFC and MFC films.     

Functional inorganic nanofillers for transparent polymers

The integration of inorganic nanoparticles into polymers has been used for the functionalization of polymer materials with great success. Whereas in traditional polymer composites, micron sized particles or agglomerates typically cause significant light scattering hampering optical applications, in nanocomposites the particle dimensions are small enough for the production of highly transparent composites. A challenge for the generation of such materials is to develop an integrated synthesis strategy adapting particle generation, surface modification and integration inside the polymer. Surface grafting using polymerizable surfactants or capping agents allows for linking the particles to the polymer. Novel techniques such as in situ polymerization and in situ particle processing are beneficial to avoid aggregation of inorganic particles inside the polymer matrix. The functions associated with inorganic fillers are widespread. Layered silicates and related materials are nowadays commercially available for improving mechanical and barrier properties in packaging. With the availability of highly transparent materials, the focus has shifted towards optical functions such as luminescence and UV-protection in transparent polymers. IR-active fillers are used in laser-holography for transparent poly(methyl methacrylate) (PMMA) nanocomposites. Refractive index modulation and ultrahigh refractive index films were developed based on inorganic materials such as PbS. The integration of magnetic nanoparticles has a great potential for applications such as electromagnetic interference shielding and magneto-optical storage.This tutorial review will summarize functions associated with the integration of inorganic nanofillers in polymers with a focus on optical properties.