Polymers

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7 pages, 215 KiB

Open AccessEditorial

Rheology and Processing of Polymers

by Khalid Lamnawar and Abderrahim Maazouz

Polymers 2022, 14(12), 2327; https://doi.org/10.3390/polym14122327 - 8 Jun 2022

Cited by 1 | Viewed by 2545

Abstract

I am so glad to share with you our Special Issue entitled ‘Rheology and Processing of Polymers’, which covers the latest developments in the field of rheology and polymer processing, highlighting cutting-edge research focusing on the processing of advanced polymers and their composites [...] Read more.

I am so glad to share with you our Special Issue entitled ‘Rheology and Processing of Polymers’, which covers the latest developments in the field of rheology and polymer processing, highlighting cutting-edge research focusing on the processing of advanced polymers and their composites [...] Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

Research

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13 pages, 3013 KiB

Open AccessArticle

Fluorinated Ethylene Propylene Coatings Deposited by a Spray Process: Mechanical Properties, Scratch and Wear Behavior

by Najoua Barhoumi, Kaouther Khlifi, Abderrahim Maazouz and Khalid Lamnawar

Polymers 2022, 14(2), 347; https://doi.org/10.3390/polym14020347 - 17 Jan 2022

Cited by 14 | Viewed by 3229

Abstract

To increase the lifetime of metallic molds and protect their surface from wear, a fluorinated ethylene propylene (FEP) polymer was coated onto a stainless-steel (SS304) substrate, using an air spray process followed by a heat treatment. The microstructural properties of the coating were [...] Read more.

To increase the lifetime of metallic molds and protect their surface from wear, a fluorinated ethylene propylene (FEP) polymer was coated onto a stainless-steel (SS304) substrate, using an air spray process followed by a heat treatment. The microstructural properties of the coating were studied using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) as well as X-ray diffraction. The mechanical properties and adhesion behavior were analyzed via a nanoindentation test and progressive scratching. According to the results, the FEP coating had a smooth and dense microstructure. The mechanical properties of the coatings, i.e., the hardness and Young’s modulus, were 57 ± 2.35 and 1.56 ± 0.07 GPa, respectively. During scratching, successive delamination stages (initiation, expansion, and propagation) were noticed, and the measured critical loads L_C1 (3.36 N), L_C2 (6.2 N), and L_C3 (7.6 N) indicated a high adhesion of the FEP coating to SS304. The detailed wear behavior and related damage mechanisms of the FEP coating were investigated employing a multi-pass scratch test and SEM in various sliding conditions. It was found that the wear volume increased with an increase in applied load and sliding velocity. Moreover, the FEP coating revealed a low friction coefficient (around 0.13) and a low wear coefficient (3.1 × 10⁻⁴ mm³ N m⁻¹). The investigation of the damage mechanisms of the FEP coating showed a viscoelastic plastic deformation related to FEP ductility. Finally, the coating’s resistance to corrosion was examined using electrochemical measurements in a 3.5 wt% NaCl solution. The coating was found to provide satisfactory corrosion protection to the SS304 substrate, as no corrosion was observed after 60 days of immersion. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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13 pages, 1826 KiB

Open AccessEditor’s ChoiceArticle

Applicability of the Cox-Merz Rule to High-Density Polyethylene Materials with Various Molecular Masses

by Raffael Rathner, Wolfgang Roland, Hanny Albrecht, Franz Ruemer and Jürgen Miethlinger

Polymers 2021, 13(8), 1218; https://doi.org/10.3390/polym13081218 - 9 Apr 2021

Cited by 8 | Viewed by 3407

Abstract

The Cox-Merz rule is an empirical relationship that is commonly used in science and industry to determine shear viscosity on the basis of an oscillatory rheometry test. However, it does not apply to all polymer melts. Rheological data are of major importance in [...] Read more.

The Cox-Merz rule is an empirical relationship that is commonly used in science and industry to determine shear viscosity on the basis of an oscillatory rheometry test. However, it does not apply to all polymer melts. Rheological data are of major importance in the design and dimensioning of polymer-processing equipment. In this work, we investigated whether the Cox-Merz rule is suitable for determining the shear-rate-dependent viscosity of several commercially available high-density polyethylene (HDPE) pipe grades with various molecular masses. We compared the results of parallel-plate oscillatory shear rheometry using the Cox-Merz empirical relation with those of high-pressure capillary and extrusion rheometry. To assess the validity of these techniques, we used the shear viscosities obtained by these methods to numerically simulate the pressure drop of a pipe head and compared the results to experimental measurements. We found that, for the HDPE grades tested, the viscosity data based on capillary pressure flow of the high molecular weight HDPE describes the pressure drop inside the pipe head significantly better than do data based on parallel-plate rheometry applying the Cox-Merz rule. For the lower molecular weight HDPE, both measurement techniques are in good accordance. Hence, we conclude that, while the Cox-Merz relationship is applicable to lower-molecular HDPE grades, it does not apply to certain HDPE grades with high molecular weight. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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18 pages, 3126 KiB

Open AccessArticle

Shear and Extensional Rheology of Linear and Branched Polybutylene Succinate Blends

by Violette Bourg, Rudy Valette, Nicolas Le Moigne, Patrick Ienny, Valérie Guillard and Anne Bergeret

Polymers 2021, 13(4), 652; https://doi.org/10.3390/polym13040652 - 22 Feb 2021

Cited by 18 | Viewed by 3891

Abstract

The molecular architecture and rheological behavior of linear and branched polybutylene succinate blends have been investigated using size-exclusion chromatography, small-amplitude oscillatory shear and extensional rheometry, in view of their processing using cast and blown extrusion. Dynamic viscoelastic properties indicate that a higher branched [...] Read more.

The molecular architecture and rheological behavior of linear and branched polybutylene succinate blends have been investigated using size-exclusion chromatography, small-amplitude oscillatory shear and extensional rheometry, in view of their processing using cast and blown extrusion. Dynamic viscoelastic properties indicate that a higher branched polybutylene succinate amount in the blend increases the relaxation time due to an increased long-chain branching degree. Branched polybutylene succinate exhibits pronounced strain hardening under uniaxial elongation, which is known to improve processability. Under extensional flow, the 50/50 wt % blend exhibits the same behavior as linear polybutylene succinate. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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15 pages, 5443 KiB

Open AccessArticle

Substantial Effect of Water on Radical Melt Crosslinking and Rheological Properties of Poly(ε-Caprolactone)

by Angelica Avella, Rosica Mincheva, Jean-Marie Raquez and Giada Lo Re

Polymers 2021, 13(4), 491; https://doi.org/10.3390/polym13040491 - 4 Feb 2021

Cited by 17 | Viewed by 3558

Abstract

One-step reactive melt processing (REx) via radical reactions was evaluated with the aim of improving the rheological properties of poly(ε-caprolactone) (PCL). In particular, a water-assisted REx was designed under the hypothesis of increasing crosslinking efficiency with water as a low viscous medium in [...] Read more.

One-step reactive melt processing (REx) via radical reactions was evaluated with the aim of improving the rheological properties of poly(ε-caprolactone) (PCL). In particular, a water-assisted REx was designed under the hypothesis of increasing crosslinking efficiency with water as a low viscous medium in comparison with a slower PCL macroradicals diffusion in the melt state. To assess the effect of dry vs. water-assisted REx on PCL, its structural, thermo-mechanical and rheological properties were investigated. Water-assisted REx resulted in increased PCL gel fraction compared to dry REx (from 1–34%), proving the rationale under the formulated hypothesis. From dynamic mechanical analysis and tensile tests, the crosslink did not significantly affect the PCL mechanical performance. Dynamic rheological measurements showed that higher PCL viscosity was reached with increasing branching/crosslinking and the typical PCL Newtonian behavior was shifting towards a progressively more pronounced shear thinning. A complete transition from viscous- to solid-like PCL melt behavior was recorded, demonstrating that higher melt elasticity can be obtained as a function of gel content by controlled REx. Improvement in rheological properties offers the possibility of broadening PCL melt processability without hindering its recycling by melt processing. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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21 pages, 6240 KiB

Open AccessArticle

Multi-Micro/Nanolayer Films Based on Polyolefins: New Approaches from Eco-Design to Recycling

by Geraldine Cabrera, Ibtissam Touil, Emna Masghouni, Abderrahim Maazouz and Khalid Lamnawar

Polymers 2021, 13(3), 413; https://doi.org/10.3390/polym13030413 - 28 Jan 2021

Cited by 15 | Viewed by 3593

Abstract

This paper describes a future-oriented approach for the valorization of polyethylene-based multilayer films. The method involves going from eco-design to mechanical recycling of multilayer films via forced assembly coextrusion. The originality of this study consists in limiting the number of constituents, reducing/controlling the [...] Read more.

This paper describes a future-oriented approach for the valorization of polyethylene-based multilayer films. The method involves going from eco-design to mechanical recycling of multilayer films via forced assembly coextrusion. The originality of this study consists in limiting the number of constituents, reducing/controlling the thickness of the layers and avoiding the use of tie layers. The ultimate goal is to improve the manufacturing of new products from recycled multilayer materials by simplifying their recyclability. Within this framework, new structures were developed with two polymer systems: polyethylene/polypropylene and polyethylene/polystyrene, with nominal micro- and nanometric thicknesses. Hitherto, the effect of the multi-micro/nanolayer architecture as well as initial morphological and mechanical properties was evaluated. Several recycling processes were investigated, including steps such as: (i) grinding; (ii) monolayer cast film extrusion; or (iii) injection molding with or without an intermediate blending step by twin-screw extrusion. Subsequently, the induced morphological and mechanical properties were investigated depending on the recycling systems and the relationships between the chosen recycling processes or strategies, and structure and property control of the recycled systems was established accordingly. Based on the results obtained, a proof of concept was demonstrated with the eco-design of multi-micro/nanolayer films as a very promising solution for the industrial issues that arise with the valorization of recycled materials. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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13 pages, 5572 KiB

Open AccessArticle

Fabrication of Drug-Eluting Nano-Hydroxylapatite Filled Polycaprolactone Nanocomposites Using Solution-Extrusion 3D Printing Technique

by Pang-Yun Chou, Ying-Chao Chou, Yu-Hsuan Lai, Yu-Ting Lin, Chia-Jung Lu and Shih-Jung Liu

Polymers 2021, 13(3), 318; https://doi.org/10.3390/polym13030318 - 20 Jan 2021

Cited by 25 | Viewed by 3485

Abstract

Polycaprolactone/nano-hydroxylapatite (PCL/nHA) nanocomposites have found use in tissue engineering and drug delivery owing to their good biocompatibility with these types of applications in addition to their mechanical characteristics. Three-dimensional (3D) printing of PCL/nHA nanocomposites persists as a defiance mostly because of the lack [...] Read more.

Polycaprolactone/nano-hydroxylapatite (PCL/nHA) nanocomposites have found use in tissue engineering and drug delivery owing to their good biocompatibility with these types of applications in addition to their mechanical characteristics. Three-dimensional (3D) printing of PCL/nHA nanocomposites persists as a defiance mostly because of the lack of commercial filaments for the conventional fused deposition modeling (FDM) method. In addition, as the composites are prepared using FDM for the purpose of delivering pharmaceuticals, thermal energy can destroy the embedded drugs and biomolecules. In this report, we investigated 3D printing of PCL/nHA using a lab-developed solution-extrusion printer, which consists of an extrusion feeder, a syringe with a dispensing nozzle, a collection table, and a command port. The effects of distinct printing variables on the mechanical properties of nanocomposites were investigated. Drug-eluting nanocomposite screws were also prepared using solution-extrusion 3D printing. The empirical outcomes suggest that the tensile properties of the 3D-printed PCL/nHA nanocomposites increased with the PCL/nHA-to-dichloromethane (DCM) ratio, fill density, and print orientation but decreased with an increase in the moving speed of the dispensing tip. Furthermore, printed drug-eluting PCL/nHA screws eluted high levels of antimicrobial vancomycin and ceftazidime over a 14-day period. Solution-extrusion 3D printing demonstrated excellent capabilities for fabricating drug-loaded implants for various medical applications. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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9 pages, 1532 KiB

Open AccessEditor’s ChoiceArticle

Effect of Material Parameter of Viscoelastic Giesekus Fluids on Extensional Properties in Spinline and Draw Resonance Instability in Isothermal Melt Spinning Process

by Geunyeop Park, Jangho Yun, Changhoon Lee and Hyun Wook Jung

Polymers 2021, 13(1), 139; https://doi.org/10.3390/polym13010139 - 31 Dec 2020

Cited by 2 | Viewed by 3128

Abstract

The draw resonance instability of viscoelastic Giesekus fluids was studied by correlating the spinline extensional features and transit times of several kinematic waves in an isothermal melt spinning process. The critical drawdown ratios were critically dependent on the Deborah number (De, [...] Read more.

The draw resonance instability of viscoelastic Giesekus fluids was studied by correlating the spinline extensional features and transit times of several kinematic waves in an isothermal melt spinning process. The critical drawdown ratios were critically dependent on the Deborah number (De, the ratio of material relaxation time to process time) and a single material parameter (

α_{G}

) of the Giesekus fluid. In the intermediate range of

α_{G}

, the stability status changed distinctively with increasing De, i.e., the spinning system was initially stabilized and subsequently destabilized, as De increases. In this

α_{G}

regime, the level of velocity and extensional-thickening rheological property in the spinline became gradually enhanced at low De and weakened at high De. The draw resonance onsets for different values of

α_{G}

were determined precisely using a simple indicator composed of several kinematic waves traveling the entire spinline and period of oscillation. The change in transit times of kinematic waves for varying De adequately reflected the effect of

α_{G}

on the change in stability. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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24 pages, 14060 KiB

Open AccessArticle

Study of the Properties of a Biodegradable Polymer Filled with Different Wood Flour Particles

by Francisco Parres, Miguel Angel Peydro, David Juarez, Marina P. Arrieta and Miguel Aldas

Polymers 2020, 12(12), 2974; https://doi.org/10.3390/polym12122974 - 13 Dec 2020

Cited by 8 | Viewed by 3037

Abstract

Lignocellulosic wood flour particles with three different sizes were used to reinforce Solanyl^® type bioplastic in three compositions (10, 20, and 30 wt.%) and further processed by melt-extrusion and injection molding to simulate industrial conditions. The wood flour particles were morphologically and [...] Read more.

Lignocellulosic wood flour particles with three different sizes were used to reinforce Solanyl^® type bioplastic in three compositions (10, 20, and 30 wt.%) and further processed by melt-extrusion and injection molding to simulate industrial conditions. The wood flour particles were morphologically and granulometric analyzed to evaluate their use as reinforcing filler. The Fuller method on wood flour particles was successfully applied and the obtained results were subsequently corroborated by the mechanical characterization. The rheological studies allowed observing how the viscosity was affected by the addition of wood flour and to recover information about the processing conditions of the biocomposites. Results suggest that all particles can be employed in extrusion processes (shear rate less than 1000 s⁻¹). However, under injection molding conditions, biocomposites with high percentages of wood flour or excessively large particles may cause an increase in defective injected-parts due to obstruction of the gate in the mold. From a processing point of view and based on the biocomposites performance, the best combination resulted in Solanyl^® type biopolymer reinforced with wood flour particles loaded up to 20 wt.% of small and medium particles size. The obtained biocomposites are of interest for injected molding parts for several industrial applications. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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16 pages, 9992 KiB

Open AccessEditor’s ChoiceArticle

Reliability of Free Inflation and Dynamic Mechanics Tests on the Prediction of the Behavior of the Polymethylsilsesquioxane–High-Density Polyethylene Nanocomposite for Thermoforming Applications

by Fouad Erchiqui, Khaled Zaafrane, Abdessamad Baatti, Hamid Kaddami and Abdellatif Imad

Polymers 2020, 12(11), 2753; https://doi.org/10.3390/polym12112753 - 21 Nov 2020

Cited by 2 | Viewed by 2300

Abstract

Numerical modeling of the thermoforming process of polymeric sheets requires precise knowledge of the viscoelastic behavior under conjugate effect pressure and temperature. Using two different experiments, bubble inflation and dynamic mechanical testing on a high-density polyethylene (HDPE) nanocomposite reinforced with polymethylsilsesquioxane HDPE (PMSQ–HDPE) [...] Read more.

Numerical modeling of the thermoforming process of polymeric sheets requires precise knowledge of the viscoelastic behavior under conjugate effect pressure and temperature. Using two different experiments, bubble inflation and dynamic mechanical testing on a high-density polyethylene (HDPE) nanocomposite reinforced with polymethylsilsesquioxane HDPE (PMSQ–HDPE) nanoparticles, material constants for Christensen’s model were determined by the least squares optimization. The viscoelastic identification relative to the inflation test seemed to be the most appropriate for the numerical study of thermoforming of a thin PMSQ–HDPE part. For this purpose, the finite element method was considered. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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15 pages, 5144 KiB

Open AccessArticle

TPV: A New Insight on the Rubber Morphology and Mechanic/Elastic Properties

by Cindy Le Hel, Véronique Bounor-Legaré, Mathilde Catherin, Antoine Lucas, Anthony Thèvenon and Philippe Cassagnau

Polymers 2020, 12(10), 2315; https://doi.org/10.3390/polym12102315 - 10 Oct 2020

Cited by 32 | Viewed by 6962

Abstract

The objective of this work is to study the influence of the ratio between the elastomer (EPDM) phase and the thermoplastic phase (PP) in thermoplastic vulcanizates (TPVs) as well as the associated morphology of the compression set of the material. First, from a [...] Read more.

The objective of this work is to study the influence of the ratio between the elastomer (EPDM) phase and the thermoplastic phase (PP) in thermoplastic vulcanizates (TPVs) as well as the associated morphology of the compression set of the material. First, from a study of the literature, it is concluded that the rubber phase must be dispersed with a large distribution of the domain size in the thermoplastic phase in order to achieve a high concentration, i.e., a maximal packing fraction close to ~0.80. From this discussion, it is inferred that a certain degree of progress in the crosslinking reaction must be reached when the thermoplastic phase is melted during mixing in order to achieve dispersion of the elastomeric phase in the thermoplastic matrix under maximum stress. In terms of elasticity recovery which is measured from the compression set experiment, it is observed that the crosslinking agent nature (DCP or phenolic resin) has no influence in the case of a TPV compared with a pure crosslinked EPDM system. Then, the TPV morphology and the rubber phase concentration are the first order parameters in the compression set of TPVs. Finally, the addition of carbon black fillers leads to an improvement of the mechanical properties at break for the low PP concentration (20%). However, the localization of carbon black depends on the crosslinking chemistry nature. With radical chemistry by organic peroxide decomposition, carbon black is located at the interface of EPDM and PP acting as a compatibilizer. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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15 pages, 6313 KiB

Open AccessArticle

Design and Synthesis of Polysiloxane Based Side Chain Liquid Crystal Polymer for Improving the Processability and Toughness of Magnesium Hydrate/Linear Low-Density Polyethylene Composites

by Xiaoxiao Guan, Bo Cao, Jianan Cai, Zhenxing Ye, Xiang Lu, Haohao Huang, Shumei Liu and Jianqing Zhao

Polymers 2020, 12(4), 911; https://doi.org/10.3390/polym12040911 - 14 Apr 2020

Cited by 7 | Viewed by 3150

Abstract

In this study, a polysiloxane grafted by thermotropic liquid crystal polymer (PSCTLCP) is designed and synthesized to effectively improve the processability and toughness of magnesium hydroxide (MH)/linear low-density polyethylene (LLDPE) composites. The obtained PSCTLCP is a nematic liquid crystal polymer; the liquid crystal [...] Read more.

In this study, a polysiloxane grafted by thermotropic liquid crystal polymer (PSCTLCP) is designed and synthesized to effectively improve the processability and toughness of magnesium hydroxide (MH)/linear low-density polyethylene (LLDPE) composites. The obtained PSCTLCP is a nematic liquid crystal polymer; the liquid crystal phase exists in a temperature range of 170 to 275 °C, and its initial thermal decomposition temperature is as high as 279.6 °C, which matches the processing temperature of MH/LLDPE composites. With the increase of PSCTLCP loading, the balance melt torque of MH/LLDPE/PSCTLCP composites is gradually decreased by 42% at 5 wt % PSCTLCP loading. Moreover, the power law index of MH/LLDPE/PSCTLCP composite melt is smaller than 1, but gradually increased with PSCTLCP, the flowing activation energy of PSCTLCP-1.0 is lower than that of MH/LLDPE at the same shear rate, indicating that the sensitivity of apparent melt viscosity of the composites to shear rate and to temperature is decreased with the increase of PSCTLCP, and the processing window is broadened by the addition of PSCTLCP. Besides, the elongation at break of MH/LLDPE/PSCTLCP composites increases from 6.85% of the baseline MH/LLDPE to 17.66% at 3 wt % PSCTLCP loading. All the results indicate that PSCTLCP can significantly improve the processability and toughness of MH/LLDPE composites. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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21 pages, 8831 KiB

Open AccessArticle

Comparison of the Foamability of Linear and Long-Chain Branched Polypropylene—The Legend of Strain-Hardening as a Requirement for Good Foamability

by Nick Weingart, Daniel Raps, Mingfu Lu, Lukas Endner and Volker Altstädt

Polymers 2020, 12(3), 725; https://doi.org/10.3390/polym12030725 - 24 Mar 2020

Cited by 28 | Viewed by 5823

Abstract

Polypropylene (PP) is an outstanding material for polymeric foams due to its favorable mechanical and chemical properties. However, its low melt strength and fast crystallization result in unfavorable foaming properties. Long-chain branching of PP is regarded as a game changer in foaming due [...] Read more.

Polypropylene (PP) is an outstanding material for polymeric foams due to its favorable mechanical and chemical properties. However, its low melt strength and fast crystallization result in unfavorable foaming properties. Long-chain branching of PP is regarded as a game changer in foaming due to the introduction of strain hardening, which stabilizes the foam morphology. In this work, a thorough characterization with respect to rheology and crystallization characteristics of a linear PP, a PP/PE-block co-polymer, and a long-chain branched PP are conducted. Using these results, the processing window in foam-extrusion trials with CO₂ and finally the foam properties are explained. Although only LCB-PP exhibits strain hardening, it neither provide the broadest foaming window nor the best foam quality. Therefore, multiwave experiments were conducted to study the gelation due to crystallization and its influence on foaming. Here, linear PP exhibited a gel-like behavior over a broad time frame, whereas the other two froze quickly. Thus, apart from strain hardening, the crystallization behavior/crystallization kinetics is of utmost importance for foaming in terms of a broad processing window, low-density, and good morphology. Therefore, the question arises, whether strain hardening is really essential for low density foams with a good cellular morphology. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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Review

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33 pages, 7215 KiB

Open AccessReview

A Journey from Processing to Recycling of Multilayer Waste Films: A Review of Main Challenges and Prospects

by Geraldine Cabrera, Jixiang Li, Abderrahim Maazouz and Khalid Lamnawar

Polymers 2022, 14(12), 2319; https://doi.org/10.3390/polym14122319 - 8 Jun 2022

Cited by 28 | Viewed by 8626

Abstract

In a circular economy context with the dual problems of depletion of natural resources and the environmental impact of a growing volume of wastes, it is of great importance to focus on the recycling process of multilayered plastic films. This review is dedicated [...] Read more.

In a circular economy context with the dual problems of depletion of natural resources and the environmental impact of a growing volume of wastes, it is of great importance to focus on the recycling process of multilayered plastic films. This review is dedicated first to the general concepts and summary of plastic waste management in general, making emphasis on the multilayer films recycling process. Then, in the second part, the focus is dealing with multilayer films manufacturing process, including the most common materials used for agricultural applications, their processing, and the challenges of their recycling, recyclability, and reuse. Hitherto, some prospects are discussed from eco-design to mechanical or chemical recycling approaches. Full article

(This article belongs to the Special Issue Rheology and Processing of Polymers)

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