CLEAN - Valorizing Sustainable Plastics through a CLEver use of NANoparticles

CLEAN is a project funded by the Italian Ministry of University and Research (MUR) in the framework of the call PRIN: Progetti di Ricerca di Rilevante Interesse Nazionale («Research Projects of Relevant National Interest»)

CLEAN aims at providing sustainable alternatives to ubiquitous petroleum-based plastics through an innovative use of nanoparticles, which are used as a clever tool for manipulating the microstructure and, through it, the properties of blends of bio-based polymers and/or recycled plastics.

CLEAN proves that a clever nanoparticle-assisted materials design can lead to green formulations able to compete with petroleum-based plastics in terms of costs and properties.

Rather than using nanoparticles or blending polymers, CLEAN combines nanoparticles and polymer blending, looking for synergic effects.

To obtain blends with a prescribed morphology and, hence, with a desired set of properties, a multi-scale approach is strictly needed to bridge the gap between the micro- and macro-scale.

CLEAN - Main activities

1. Synthesis and Modification of Nanoparticles (NPs).
   The Research Unit (RU) UniCt and CNR worked on the synthesis of nanostructures of metallic oxides, such as ZnO, using the Chemical Bath Deposition (CBD) technique. UniCt also collaborated with other units in the morphological characterization of NPs and polymer nanocomposite blends. The RU-CNR worked on the surface modification of ZnO nanoparticles and conducted studies on the characterization of polymer nanocomposites loaded with various nanoparticles and examined the effects of temperature, seawater degradation, and UV exposure.
   
   RU-UniCt (co-leader of activity 1 - Synthesis and Modification of Nanoparticles (NPs)

   1. Focused on synthesizing nanostructures of metallic oxides, such as ZnO and WO3, with controlled morphologies and dimensions using the Chemical Bath Deposition (CBD) technique.
   2. Characterized the obtained nanoparticles (NPs) through scanning electron microscopy (SEM).
   3. Collaborated with UdR CNR in characterizing nanoloaded blends with n-ZnO.
   4. In collaboration with UdR UniNa, analyzed the environmental impacts of n-ZnO synthesis through Life Cycle Assessment (LCA) modeling.

   

   
   Main publications

   1. Di Mari G. M., Spadaro M. C., Salutari F., Arbiol J., Bruno L., Mineo G., ... & Mirabella S.
      Low-Cost, High-Yield Zinc Oxide-Based Nanostars for Alkaline Overall Water Splitting
      ACS omega 2023, 8(40), 37023-37031
   2. Di Mari G.M., Mineo G., Franzò G., Mirabella S., Bruno E., Strano V.
      Low-Cost, High-Yield ZnO Nanostars Synthesis for Pseudocapacitor Applications
      Nanomaterials 2022, 12, 2588

   RU-CNR (co-leader of activity 1 - Synthesis and Modification of Nanoparticles)

   1. Engaged in characterizing polymer nanocomposites loaded with nanoparticles such as titanium dioxide (n-TiO2), montmorillonite, and n-ZnO.
   2. Studied the effect of NPs on nanocomposites through thermogravimetric analysis, size exclusion chromatography, mass spectrometry, and electron microscopy.
   3. Investigated degradation phenomena in seawater and photodegradation of polymer blends.
   4. Studied the effects of NPs functionalized with stearic acid on surface compatibility and adhesion in polymer blends.

   

   
   Main publications

   1. R. Puglisi, A. A. Scamporrino, N. Tz. Dintcheva, G. Filippone, E. Bruno, P. Scarfato, P. Cerruti & S. C. Carroccio
      Photo- and Water-Degradation Phenomena of ZnO Bio-Blend Based on Poly(lactic acid) and Polyamide 11
      Polymers 2023, 15(6), 1434
   2. M. Ussia, G. Curcuruto, D. Zampino, N. Tz. Dintcheva, G. Filippone, R. Mendichi & S. C. Carroccio
      Role of Organo-Modifier and Metal Impurities of Commercial Nanoclays in the Photo- and Thermo-Oxidation of Polyamide 11 Nanocomposites
      Polymers 2020, 12(5), 1034
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2. Rheo-optical Analysis.
   The RU-UniNa performed rheo-optical analyses to shed light on the basic mechanisms of breakup, shape relaxation and coalescence responsible for the microstructural evolutions of polymer blends during flow. The research extended to industrially relevant materials, including blends with layered silicates, proving the scalability of the approaches of CLEAN.
   
   RU-UniNa (leader of activity 2):

   1. Studied the influence of thermodynamic and kinetic factors on the localization of NPs in model polymer blends.
   2. Adopted a two-step mixing protocol to achieve a preferential distribution of NPs.
   3. Conducted rheo-optical observations to analyze the rupture and coalescence phenomena of droplets in polymer blends.
   4. Explored the use of NPs to improve the microstructure and performance of incompatible blends of recycled polymers.

   

   
   Main publications

   1. S. C. Carroccio, P. Scarfato, E. Bruno, P. Aprea, N. Tz. Dintcheva, & G. Filippone
      Impact of nanoparticles on the environmental sustainability of polymer nanocomposites based on bioplastics or recycled plastics–A review of life-cycle assessment studies
      Journal of Cleaner Production 2022, 335, 130322
   2. A. Marotta, A. Causa, M. Salzano de Luna, V. Ambrogi, & G. Filippone
      Tuning the Morphology of HDPE/PP/PET Ternary Blends by Nanoparticles: A Simple Way to Improve the Performance of Mixed Recycled Plastics
      Polymers 2022, 14(24), 5390
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3. Blends of Bioderived/Biodegradable Polymers.
   The RU-UniPa focused on preparing blends of biopolymers with metallic oxide nanoparticles, examining their effects on mechanical strength and degradation.
   RU-UniPa (leader of WP3):

   1. Focused on preparing blends of biodegradable and bioderived biopolymers with the addition of metallic oxide NPs.
   2. Examined the effects of NPs on the mechanical strength and degradation of blends.
   3. Studied the pro-degrading capability of NPs, accelerating the degradation of biopolymers.
   4. Analyzed the pro-degradative mechanism of NPs through the generation of oxygenated groups.

   

   
   Main publications

   1. E. Morici, S.C. Carroccio, E. Bruno, P. Scarfato, G. Filippone, N.Tz. Dintcheva
      Recycled (bio)plastics and (bio)plastic composites: a trade opportunity in a green future
      Polymers, 14, 2038 (2022)
   
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4. Blends of Recycled Polymers.
   The RU-UniSa explored the use of nanoparticles to enhance the performance of recycled polymer blends from post-consumer urban collection. They utilized organo-modified lamellar silicates and analyzed the thermal, mechanical, and morphological properties of the blends.
   RU-UniSa (leader of activity 4):

   1. Explored the use of NPs to manipulate the microstructure and performance of incompatible blends of recycled polymers.
   2. Worked with recycled materials from post-consumer urban waste collection.
   3. Used organomodified lamellar silicates as NPs.
   4. Analyzed the composition-structure-performance relationships of nanoloaded blends.

   

   Main publications

   1. R. Ferraioli, L. Di Maio, L. Incarnato, P. Scarfato
      Development of recycled blown films based on post-consumer plastics recovered from seas and rivers
      Chemical Engineering Transactions, 86 433-438
   2. R. Ferraioli, L. Incarnato, L. Di Maio, P. Scarfato
      A preliminary study on recyclability of mixed plastic wastes recovered from urban collection
      Key Engineering Materials, 885, 109-114
   
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