The importance of the project goal arises from the rapid increase of packaging consumption and resulting waste, most of them being from synthetic polymers which are not biodegradable for hundreds of years. This project aims to replace the petrochemical based packaging materials with polymers derived from renewable biomass feedstock thus reducing the environmental pollution and providing simplified end-of-life disposal. This goal will be achieved through the use of biodegradable polyesters (polylactic acid (PLA), polyhydroxyalkanoates (PHAs)) and nanosized cellulose fillers (CN) isolated from a cheap source, namely fruit seed shell waste. Exploiting such inexpensive sources like crop waste for CN isolation and high value added products will contribute to solve the emergent problem of increased biomass and will reduce the cost of the new designed polymer nanocomposites. The new concept of “zero-waste” will be also demonstrated in this project. Innovative technological routes will be applied for the design of new advanced and fully renewable CN/biopolymers for packaging industry. Specific melt processing tests will be performed for developing high quality extrusion films and injected parts designated for niche packaging application, for example childcare products.

The specific objectives of the project FULLBIOPACK are the following:

• Setting-up optimal technological conditions for isolation of high quality cellulose nanofibers (CN) from plum and apricot seed shells waste (PASSW);
• Establishing new innovative technological routes for CN incorporation in natural polyesters;
• Characterization protocols of resulted nanocomposites in order to establish the suitability for packaging applications;
• Dissemination of scientific outcomes

The use of renewable raw materials for packaging materials will contribute to the reduction of CO₂ emissions and mitigation of negative climate changes. By exploiting such inexpensive sources like plum and apricot seed shells waste, new cellulose nanofibers with high added value will be created, additionally solving the emergent problem of increased biomass. The obtained cellulose nanofibers will be used as fillers in fully biodegradable polyester nanocomposites for niche packaging application. The implementation of this project is expected to create synergies between industries, the obtained results will be offered to small medium enterprises for developing eco-friendly packaging materials, thus improving their competitiveness. The project will attract students and graduates in cutting-edge research, will involve multidisciplinary collaborations and will increase the competitiveness of national research and development activity. Moreover, the project will open-up new research directions for emerging technologies to produce fully biodegradable packaging starting from renewable resources.

1. Frone Adriana Nicoleta – Project manager

2. Chiulan Ioana – Postdoctoral researcher

3. Radu Anita Laura - Postdoctoral researcher

4. Tofan Vlad Constantin – PhD student

5. Trica Bogdan - PhD student

6. Panaitescu Denis Mihaela - Senior researcher

7. Corobea Mihai Cosmin - Senior researcher

8. Nicolae Cristian Andi - Senior researcher

9. Nistor Cristina Lavinia - Senior researcher

10. Corduneanu Gabriela – Technician

Phase I

Title: Phase Setting-up optimal technological conditions for isolation of high quality CN from PASSW (Preliminary studies)

Period: 01/10/2015 - 30/12/2015

Phase II

Title:

Phase Setting-up optimal technological conditions for isolation of high quality CN from PASSW. Synthesis of fully biodegradable composites from the obtained CN and natural polyesters.

Period: 31/12/2015 - 30/12/2016

Summary of the activity report phases I and II

Two types of agro-industrial wastes, plum and apricot seed shells (PASSW), were subjected to different environmentally friendly pretreatments in order to remove the non-cellulosic components. FTIR and TGA analysis highlighted the structural changes of PASSW induced by the applied pretreatments. Several methods were tested, alone or in combinations, in order to obtain cellulose nanofibers (CN) from the modified PASSW. A laboratory technology for the isolation of CN has been established after the selection of the most appropriate methods. The resulted CN were characterized in terms of morphological, thermal and chemical properties. Different routes were used for the obtaining of fully biodegradable composites (NP) from the isolated CN and natural polyesters. Barrier properties and biodegradability besides thermal and mechanical properties of the obtained NP were also studied. Moreover, the optimization of polyesters based nanocomposites processability was performed in order to select the proper conditions that lead to materials suitable for the considered applications.

Phase III

Title: Development of nanocomposites (NP) based on natural polyesters and functionalized / non-functionalized cellulose nanofibers (CN)

Period: 31/12/2016 - 30/09/2017

Summary of the activity report phase III

In this phase the incorporation of nanocellulose in various natural polymers as reinforcement was studied. The cellulose nanofibers (CN) isolated from the PASSW was subjected to different chemical treatments in order to enhance the cellulose nanofibers-hydrophobic polymer interactions. In this respect, Fischer Esterification using different organic acids was employed. A technology for the development of polymer nanocomposites (NP) based on natural polyesters and functionalized/non-functionalized cellulose nanofibers (CN) was proposed. First, the efficiency of the chemical treatments was studied by FTIR, TGA, AFM and TEM. Further, the selected functionalized cellulose nanofibers were used as reinforcements in different matrices like poly(hydroxybutyrate) (PHB) and in its blends with poly(lactic acid) (PLA). The functionalized and non-functionalized cellulose nanofibers were incorporated in the polyester matrices and processed through specific techniques like melt mixing, extrusion and injection molding, which are mandatory for packaging industry. Thermal, mechanical and morphological properties of the resulted NP were evaluated in order to assess their suitability for food and non-food packaging applications.

Published papers:

1. Adriana Nicoleta Frone, Denis Mihaela Panaitescu, Ioana Chiulan, Cristian Andi Nicolae, Zina Vuluga, Catalin Vitelaru, Celina Maria Damian. The effect of cellulose nanofibers on the crystallinity and nanostructure of poly(lactic acid) composites, Journal of Materials Science, (2016) 51:9771–9791.

2. Adriana Nicoleta Frone, Ioana Chiulan, Denis Mihaela Panaitescu, Cristian Andi Nicolae, Marius Ghiurea, Ana-Maria Galan. Isolation of cellulose nanofibers from plum seed shells, structural and morphological characterization, Materials Letters 2017, 194(1):160–163

3. Ioana Chiulan, Adriana Nicoleta Frone, Denis Mihaela Panaitescu, Cristian Andi Nicolae, Roxana Trusca, Surface properties, thermal and mechanical characteristics of poly(vinyl alcohol) – starch - bacterial cellulose composite films, Accepted for Publication in Journal of Applied Polymer Science 2017, DOI: 10.1002/app.45800. 

National and international conferences:

1. Ioana Chiulan, Denis Mihaela Panaitescu, Adriana Nicoleta Frone, Vlad Tofan, Raluca Augusta Gabor, Cristian Andi Nicolae, Zina Vuluga, “Composites based on polyhydroxyalkanoates and mechanically treated bacterial cellulose”, a XXXIV-a Conferinta Nationala de Chimie, 3-7 October 2016, Calimanesti-Caciulata, Romania.

2. Adriana Nicoleta Frone, Ioana Chiulan, Denis Mihaela Panaitescu, Raluca Augusta Gabor,  Cristian Andi Nicolae, Doina Michaela Iorga, Valentin Raditoiu, “Nanocellulose structures derived from plum seed shells”, a XXXIV-a Conferinta Nationala de Chimie, 3-7 October 2016, Calimanesti-Caciulata, Romania.

3. Adriana Nicoleta Frone, Ioana Chiulan, Denis Mihaela Panaitescu, Cristian Andi Nicolae,Mihai Cosmin Corobea, Vlad Constantin Tofan, “Nanocellulose structures derived from plum seed shells”. 5th Portuguese Young Chemists Meeting (5th PYCheM) - 1st European Young Chemists Meeting (1st EYCheM), Guimaraes, Portugalia, 25-29 April 2016.

4. Ioana Chiulan, Adriana Nicoleta Frone, Denis Mihaela Panaitescu, Cristian Andi Nicolae, Cristina Lavinia Nistor, Mihaela Cristina Bunea, “Environmentally friendly method for the separation of hemicellulose and lignin from fruit waste”. 5th Portuguese Young Chemists Meeting (5th PYCheM) - 1st European Young Chemists Meeting (1st EYCheM)”, Guimaraes, Portugalia, 25-29 April 2016.

5. A. N. Frone, I.Chiulan, D.M. Panaitescu, R.A. Gabor, C.A. Nicolae, M. Ghiurea, Polyester-Based Composites Containing Cellulose Micro/Nanofibers Derived from Industrial By-products,

“Fifth International Symposium Frontiers in Polymer Science”, 17-19 Mai 2017, Sevilia, Spania

6. I. Chiulan, A.N. Frone, D.M. Panaitescu, R. Gabor, C.A. Nicolae, S.V. Raditoiu, Investigation of Cellulose Fibbers from Plum Seed Shells as Reinforcement in Aliphatic Copolyesters, “Fifth International Symposium Frontiers in Polymer Science”, 17-19 Mai 2017, Sevilia, Spania

7. Adriana Nicoleta Frone, Ioana Chiulan, Denis Mihaela Panaitescu, Zina Vuluga, Raluca-Augusta Gabor, Cristian-Andi Nicolae, Valentin Raditoiu, Cristina Nistor, Comparative Analysis of Different Mechanical-Chemical Routes to Obtain Nanocellulose from Waste, “The 9th International Conference on Advanced Materials: ROCAM 2017”, 11-14 Iulie 2017, Bucuresti, Romania;

8. Denis Panaitescu, Adriana Frone, Sorin Vizireanu, George Dinescu, Ioana Chiulan, Cristian Nicolae, Daniela Ionita, Lavinia Carpen, Cosmin Corobea, Violeta Purcar, Cellulose with Modified Surface Properties by Plasma Treatment, “The 9th International Conference on Advanced Materials: ROCAM 2017”, 11-14 Iulie 2017, Bucuresti, Romania;

9. I. Chiulan, J.M. Raquez, A.N. Frone, D.M. Panaitescu, R. Gabor, C.A. Nicolae, The Effect of Cellulose Fibers Treatment on the Performance of the Cellulose/Aliphatic Polyesters Composites, “6th International Conference on Biobased and Biodegradable Polymers (BIOPOL-2017)”, 11-13 Septembrie 2017, Mons, Belgia.

Patents:

1. Patent claim OSIM: A 100749/27.09.2017 - Process for the production of micro(nano)cellulose crystals from plum seed shells; authors: Adriana Nicoleta Frone, Ioana Chiulan and Denis Mihaela Panaitescu.