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Report

Teaser, summary, work performed and final results

Periodic Reporting for period 1 - BARBARA (Biopolymers with advanced functionalities for building and automotive parts processed through additive manufacturing)

Teaser

Summary

BARBARA aims at valorising side-stream fractions and residues from agro-food production into novel polysaccharides and functional additives.
These raw materials have been selected for the advanced functionalities they can bring to polymeric matrixes. The polysaccharides extracted in BARBARA will be compatibilised with polyesters and polyamides and then reinforced with other extracted, modified and functionalised additives to obtain bioplastic formulations adapted to current Fused Filament Fabrication (FFF) processes. The objective of BARBARA is the development of novel bio-based engineering bioplastic materials and to validate them in functional prototypes with advanced properties for the construction and the automotive sectors.
The methods explored in the project will improve the mechanical, thermal, aesthetical and cosmetical properties of existing novel biobased polymers. A number of selected demonstrators will be chosen, these will include final parts for the automotive sector and moulds and tools for hybrid manufacturing for advanced construction applications. Innovations in FFF will be validated during the project in order to enhance the performance of our biobased materials and fulfil the intensive requirements of these industrial sectors.
BARBARA will directly contribute to KPI 5 of the SIRA document (4 new advanced biobased materials) and KPI 6 (3 validated consumer products through 2 novel value chains for FFF). The BARBARA consortium involves 10 partners (5 RTD, 3 SME and 2 Large Companies) accounting to 2 BIC full members and 3 associated members. The project will last 36 months with a budget of EUR 2,711,375.

Work performed

The BARBARA partners involved in the extraction and characterization of functional additives from lemon and pomegranate agrowastes, from the residue of discarded fruits by Spanish farmers and supplied by FECOAM, are University of Alicante (UA) and CELABOR. Lemon peel can be obtained from either the juice industry or as discarded whole fruits. In the case of pomegranate, two different wastes were considered: the rinds and the peel. The UA team was in charge of developing and optimizing extraction MAE protocols at the laboratory scale for lemon and pomegranate agroresidues by using multivariate experimental designs. These protocols allow the extraction of essential oil from lemon, pigments (lemon and pomegranate), and biomordants from pomegranate (tannins and other polyphenols) as well as its functionalisation and design to be used as additives for polymers. CELABOR was responsible for the purification of the active additives and their upscaling. The optimization of chlorophylls extraction from broccoli at lab scale by MAE was also performed by UA. KTH has developed and optimized a bioprocess for the isolation of polysaccharides (starch and arabinoxylan) from corn fibre. CELABOR carried out a preliminary upscaling of the optimized temperature conditions. Commercial starches (kindly provided by CARGILL) have been used during this period to study the best approach to increase the biobased content of engineering biopolymers. These benchmarks will be substituted by CELABORÂ´s up-scaled ones, once the up-scaling task finishes. Carbohydrate chemistry offers various reaction routes to achieve this. In parallel to the chemical modification of starch, grafting to approaches of engineering polymers onto starch have been implemented by TECNO and UNIPG in collaboration with KTH using reactive extrusion. The focus of this task has been the compatibilization of thermoplastic starch with different polyamide (PROMYDE) and INZEA grades provided by NUREL. UA has also worked on the optimization of suitable and effective functionalisation methods to modify the biomolecules previously extractede, enhancing colour, mechanical and thermal stability. Also, water/ethanol mixtures were studied to obtain the intercalated nanoclays at room temperature with the addition of surface modifiers like biomordants, to improve the nanoclay-dye interactions.
TECNO in cooperation with AITIIP, has tested different biopolyester (INZEA) and polyamide (PROMYDE) grades through filament spooling and FFF 3D printing in order to select the best candidates adequate to be the base matrix for the project bioplastic blends. Additionally, AITIIP has started the design of the FFF heading device part of which includes troubleshooting the first challenges related to the plasma implementation.
Concerning exploitation, a first definition of Key Exploitable Results and the ownership and exploitation rights has started to be discussed among partners, while some of the business plans have been further developed (e.g. new filaments, by TECNO; and the heading device, by AITIIP). Dealing with the evaluation of environmental performance of benchmarks, new products and their comparative analysis, by using LCA approaches and the analysis of the cost related to the life cycle scheme â€“ LCC, UNIPG has detailed to partners different inventory templates and the methodology to be followed in both analyses.

Key results include:
Microwave-assisted extraction of bioadditives from lemon and pomegranate:
- Bioadditives 1: Natural dyes from lemon and pomegranate agrowaste
- Bioadditives 2: Essential oil from lemon peels
- Bioadditives 3: Biomordants from pomegranate husk residue
Polyamide based formulations:
â€¢ Polyamide based formulation + modified starch
â€¢ Polyamide based + nanoclays (best thermal and mechanical properties)
Biopolyester based formulations:
â€¢ Polyester based formulation + (modified starch) + colour (dyes incorporated in nanoclays) (best aesthetical properties)

Final results

A number of key results are expected until the end of the Project: (1) Subcritical water extraction of arabinoxylan from corn fibre, (2) Functionalized nano-pigments (clays plus dyes), antimicrobials and essential oils, (3) Functionalised bio based filament for FFF process, (4) Heading device, (5) our automotive part, (6) our construction parts (moulds for RTM).
Some key strengths, relevant for the impact of the Project:
1. The results during this period, especially in terms of the new colours obtained (extracted from lemon and pomegranate agroresidues and functionalised with nanoclays), have recently changed FIAT point of view about the colour specifications. These (especially the ones coming from the pomegranate) are so novel and unique that will be conceived as new colours for a new FIAT product promoting the natural and biobased character. From the battery of colours obtained 3 have been selected for upscaling purposes (to achieve demonstrators): 1 yellowish-gold, 1 pinkish and 1 greyish-silver.
2. AITIIP and TECNO have detected the key players in the industrial FFF technology and the filaments. One of these key players for industrial market applications (high-tech) is STRATASYS, who are interested in the outcomes of BARBARA for a potential commercial release.