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Cellulosic Materials – Processing, Properties and Promising Applications Joint Working Groups & Management Committee Meetings September 22-23, 2016 Budapest COST ACTION FP1205 BUDAPEST 22-23 September 2016 Cellulosic Materials – Processing, Properties and Promising Applications Joint Working Groups & Management Committee Meetings September 22-23, 2016 Venue Rubin Wellness & Conference Hotel, Akvamarin Room Dayka Gábor u. 3. H-1118 Budapest Budapest University of Technology and Economics Budapest University of Technology and Economics Faculty of Chemical Technology and Biotechnology Department of Physical Chemistry and Materials Science Budapest, Hungary COST ACTION FP1205 BUDAPEST 22-23 September 2016 WELCOME Most welcome everyone to Budapest to join us in the upcoming joint working groups and management committee meeting within the Cost Action FP1205 “Innovative Applications of Regenerated Wood Cellulose Fibres” chaired by Dr. Åsa Östlund. The working groups meeting will run from the morning of Thursday the 22nd of September until lunch time on Friday the 23rd of September 2016. Subsequently, the 6th Management Committee meeting starts after lunch on Friday. The aim of the workshop is to provide support on new product area development around the theme “Cellulosic materials - processing, properties and promising applications” related to COST FP1205 and to spread the knowledge to the wider scientific community on the current and upcoming commercial processes as well as some of the most promising methods identified in the first 3 years of the Action. The workshop will comprise of selected keynote speakers to show their recent developments, and how these have been linked to the COST Action. The agenda will cover key activities from each Working Group in the Action as well as develop follow up on ideas for the end of the Action. These ideas will then be presented at the Management Committee for consideration and adoption during the final period of the Action. Budapest Unversity of Technology and Economics The university and the Department of Physical Chemistry and Materials Science will be introduced shortly at the beginning of the conference on Thursday. Budapest Budapest is undoubtedly one of the most beautifully located cities in the world. Buda is built on a hill on the west bank of the river Danube and forms the historical part of the city. Pest stands on a plain and it is more businesslike with its shops and boulevards. 5 AGENDA COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST FP1205 Meeting Budapest, Hungary September 22-23, 2016 Workshop on: Cellulosic materials - processing, properties and promising applications Budapest University of Technology and Economics (BME) Faculty of Chemical Technology and Biotechnology Department of Physical Chemistry and Materials Science AGENDA Day 1. Thursday - September 22, 2016 08:30 Registration 09:00 Åsa Östlund (SP, SE) and Emília Csiszár (BME, HU) Krisztina László – Vice-Rector for International Affairs Budapest University of Technology and Economics Alfréd Menyhárd - Head of Laboratory Laboratory of Plastics and Rubber Technology Department of Physical Chemistry and Materials Science Welcome Session 1 - KEYNOTE LECTURE 1 9:20 Thomas Rosenau (BOKU, AT): Towards a better understanding of cellulose swelling, dissolution, regeneration and phase transition (cellulose I II) on the molecular level 10:20 Coffee SESSION 1: ORAL PRESENTATIONS 10:40 Ulf Germgård (Karlstad University, SE): Integration of a sulfite pulp mill and a viscose plant 11:00 Nandual Wanasekara (University of Exeter, UK): Molecular deformation and orientation in ionic liquid spun cellulose fibers 11:20 Paola Orsolini (EMPA, CH): Dense and porous nanofibrillated cellulose substrates POSTER PRESENTATIONS I 11:40 P1 – Tal Ben Shalom (The Hebrew University of Jerusalem, IL): Novel environmental friendly new method for crosslinking of cellulose nanocrystals (CNCs) via esterification P2 – Arthur Werner (Univ. Bordeaux, FR): A novel method to produce polymer nanolatexes by Pickering emulsification with cellulose nanocrystals (CNCs) P3 – Vanja Kokol (Univ. Maribor, SI): In situ synthesised NanoCellulose – Hydroxyapatite based composites for phenol and cobalt adsorption COST ACTION FP1205 BUDAPEST 22-23 September 2016 P4 – Mariusz Mamiński (Warsaw University of Life Sciences, Pl): Cellulose degradation products as a raw material for PUR foams P5 – Levente Csóka (University of West Hungary, HU): Surface chemistry of sonochemically-treated bacterial cellulose P6 – Chiara Bongio (Politecnico di Milano, IT): Bacterial nanocellulose glycidylmethacrylate grafting. Preparation and perspective P7 – Kay Hettrich (Fraunhofer Institute for Applied Polymer Research, DE): Preparing of nanoparticles from partly derivatized cellulose P8 – Renata Toczyłowska-Mamińska (Warsaw University of Life Sciences, Pl): Perspective use of solubilised cellulose in microbial fuel cells (MFCs) P9 – Zvi Shtein (The Hebrew University of Jerusalem, IL): Spider silk-CBD-CNC composites: mechanism of assembly P10 – Sebestyén Nagy (Budapest University of Technology and Economics, HU): Production and properties of nanocrystalline cellulose suspensions and films 12:00 Lunch and Posters SESSION 2: KEYNOTE LECTURE 2 13:45 Stephen Eichhorn (University of Exeter, UK): Electrospun nano-fibres for bio inspired composite materials and innovative industrial applications SESSION 2: ORAL PRESENTATION 14:45 Jose M. Lagaron (Novel Materials and Nanotechnology Group, IATA-CSIC, ES): Nanocellulose to taylor the barrier performance of electrospun biopolyester coatings and layers for food packaging applications 15:25 Coffee and Posters SESSION 2: ORAL PRESENTATIONS 16:00 Eduardo Robles (University of the Basque Country UPV/EHU, ES): Heterogeneous silanization of cellulose nanofibers with 3-aminopropyl triethoxysilane 16:20 Victor Kisonen (Bi-Co, FI): Cellulose in horticultural applications 16:40 End of Day 1 17:00 Walk in the city - optional (From Szt. Gellért square either up to the Citadella or to the campus of BME) 19:30 Conference Dinner 1 2 8 9 COST ACTION FP1205 BUDAPEST 22-23 September 2016 Day 2. Friday – September 23, 2016 Session 3 - KEYNOTE LECTURE 3 9:00 Kristiina Oksman (Luleå University of Technology, SE) Cellulose nanofibers from industrial residues and their use in composite materials SESSION 3: ORAL PRESENTATIONS 10:00 Marc Delgado-Aguilar(University of Girona, ES): Hydrophobic nanocellulose-based aerogels for selective oil removal: an effective and simple method POSTER PRESENTATIONS II 10:20 P11 – Benjamin Dhuiège (University of Bordeaux, LCPO, FR): Synthesis and characterisation of nanocellulose aerogels for the elaboration of innovative and biosourced bone substitutes P12 – Linda Vecbiskena (Latvian State Institute of Wood Chemistry, LV) 100% recycled paper packaging materials: processing, properties and potential application P13 – Alena Šišková (Polymer Institute of Slovak Academy of Sciences, SK): Cellulosebased controlled-release agrochemicals formulation P14 – Alican Gençe (KU Leuven, BE): Influence of the particle concentration and Marangoni flow on the formation of cellulose nanocrystal films P15 – Tufan Salan (Kahramanmaras Sutcu Imam University, TR): Bio-based foams from renewable and sustainable polyols obtained by liquefaction of lignocellulosics P16 – Bianca-Ioana Dogaru (Petru Poni Institute of Macromolecular Chemistry, RO): Analytical methods for the investigation of the water - biodegradable films interaction P17 – Imola Herceg (Budapest University of Technology and Economics, HU): Interaction of water with CNC films P18 – David Leibler (Hebrew University of Jerusalem, IL): Nanocomposite films based on cellulose nanocrystals and titanium dioxide nanoparticles P19 – Amit Rivkin (Hebrew University of Jerusalem, IL): Bio-inspired nanocomposite films and foams from resilin-CBD bound to cellulose nanocrystals 10:40 Coffee and Posters SESSION 3: ORAL PRESENTATIONS 11:00 Helena Oliver-Ortega (Universitat de Girona, ES): Preliminary results of the application of carboxymethylated cellulose as a reinforcing agent in papermaking 11:20 Noemi Merayo (Complutense University of Madrid, ES): Relevance of retention systems when using cellulose nanofibers as strength additives in papermaking 12:00 End of Workshop Lunch MANAGEMENT COMMITTEE MEETING Participants: MC members and MC substitutes (all visitors are welcome but only MC members’ votes counts in decision making) 13:30 Åsa Östlund (SP, SE) 15:30 End of meeting 3 10 ABSTRACTS COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 1 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 1 22-23 September 2016 Towards a better understanding of cellulose swelling, dissolution, regeneration and phase transition (cellulose I II) on the molecular level mercerization with concentrated lye. It is commonly accepted that in cellulose the chains are in parallel arrangement, while cellulose II has an antiparallel chain orientation. The transition from parallel cellulose I to antiparallel cellulose II can be easily understood if the 'detour' via completely dissolved cellulose is involved: the cellulose chains are separated in solution and will re-aggregate as the thermodynamically most stable allomorph, which is cellulose II. However, how the parallel-to-antiparallel transition in solid state (during mercerization) can be imagined is still a mystery and one of the oldest riddles in cellulose science. We will add some pieces to the jigsaw puzzle of the solid-state cellulose I to cellulose II transition (evidently without being able to arrange those pieces into a final, nicely ordered picture), in particular addressing the axiom that always cellulose II is regenerated from cellulose solutions. It will be demonstrated that special regeneration conditions that align the reducing ends to one side through temporary derivative formation allow reprecipitating cellulose I from solution, independent of whether a cellulose I substrate (such as a cellulosic pulp or cotton linters) or a cellulose II substrate (such as viscose fibers) had been dissolved. The latter case represents something like a 'reverse mercerization' with regard to the allomorph change. The experiments involve different cellulosic substrates, and the transitions are studied by means of solution and solid-state NMR, light scattering as well as X-ray diffraction experiments. Thomas Rosenau,1 Antje Potthast,1 Markus Bacher,1 Fumiaki Nakatsubo,2 Alfred D. French,3 Bob Blant,4 Kanji Kajiwara,5 Kurt Mereiter6 1 BOKU University Vienna, Austria, Department of Chemistry, Division of Chemistry of 2 Renewable Resources; Lab of Active Bio-based Materials, Kyoto University, Japan; Kyoto 3 University, Japan, Uji Research Center; Southern Regional Research Center, U.S. 4 5 Department of Agriculture, Metairie, Louisiana, USA; Shinshu University, Japan; Harvard 6 Nanorobotics Center, USA; Vienna University of Technology, Austria Keywords: cellulose, dissolution, H-bond system, phase transition, swelling, regeneration ABSTRACT The exact structure of the hydrogen bond networks and the changes of these networks upon swelling and dissolution processes are current ‘hot topics’ in cellulose research. Hbonds are responsible for the allomorphism of cellulose, for the typical properties of cellulose, and for reactivity and chemical behavior. The use of isotopic labeling with modern solid-state NMR techniques in combination with X-ray crystal structure analysis is a powerful approach to obtain solid state and gel structural data of cellulose and cellulose model compounds, so that we now come closer to an understanding of cellulose swelling and dissolution on a molecular level, and might even successfully address the old and unanswered question about the special nature of cellulose solvents. With the 13C-perlabeled solutes (cellulose model compounds and celluloses), novel solid-state NMR experiments that were based on the high degree of isotopic enrichment (>99%) became possible. Protons in hydrogen bonds (C-O-H…O-C motifs) are detected through the two carbons that are bridged by this proton. The cleavage and re-formation of the complex hydrogen bond network became accessible to detailed analysis for the first time. We selected the following cellulose solvents for our studies, which were synthesized in perdeuterated and 15N-labeled form: NMMO, DMAc, and BMIM acetate. 15 N-labeling in addition to perdeuteration allows measuring the defined distance between solvent nitrogen and the respective cellulose (model) carbon, and thus monitoring approach and action of the solvent. The studies showed that swelling is a reversible process of 3-4 stages, connected with cleavage of hydrogen bonds mainly to/from OH-6 and OH-2. Dissolution, by contrast, is irreversible and involves in addition H-bonds to/from OH-3. In addition to common O-H hydrogen bonds, cellulose solvents also form non-conventional C-H hydrogen bonds, involving exclusively CH-1 and CH-3, but no other carbon positions, which might be a prerequisite to cellulose dissolution. All these molecular level data are available for the first time and provide a consistent picture of the molecular mechanisms of swelling and dissolution of cellulose and cellulosic model compounds, which will be presented in this lecture. The allomorphism of cellulose is a wellknown fact. Cellulose I and cellulose II are the most important allomorphs, the former term describing 'native' cellulose, the latter being cellulose that has either been regenerated from cellulose solutions or obtained by 12 13 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 1 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 1 22-23 September 2016 RESULTS AND DISCUSSION Integration of a sulfite pulp mill and a viscose plant Hans Magnusson, Gunnar Henriksson, Ulf Germgård The four pulping alternatives for sulfite dissolving pulp production integrated with a traditional viscose plant are shown in a simplified manner in Fig.1. Karlstad University, Department of Engineering and Chemical Sciences, SE 65188 Karlstad, Sweden, [email protected], [email protected]. [email protected] Keywords: integration, magnesium, sodium, sulfite pulp, viscose ABSTRACT Protection of our global environment has become an important issue for more and more people and it is today well accepted in all countries that the pollution of our environment must go down if we are going to survive. One way to reduce the impact on our environment is to reuse matter and products that earlier were considered as being waste products. These were thrown away even if they were possible to use much longer. The same goes for industrial waste streams which often have been sent to the sewer even though they have contained many useful products which could have been reused many times. Thus the global population increases and so does the wealth of the people and especially so for the middle class both in the developed and the developing countries. This has resulted in a situation that for example China is now consuming more products and energy than the whole of Europe. More people with more money to spend means that an increasing number of products are consumed and this is good for the business life but very bad for the environment. The increasing purchasing power has considerably raised for example the consumption of textiles and the increase in the demand is assumed to continue during the next 30-50 years. At the same time is the possibility to considerably increase the production of cotton non-existing of several reasons and to increase the production of oil based textile fibers is also problematic as this will lead to increasing carbon dioxide emissions. One way to solve this dilemma is to base future textile production to a high degree on sustainable raw materials for example cellulose from trees in the forests. Such cellulose can be used to produce for example conventional viscose but the viscose process is by tradition both very polluting leading to both emissions that can catch fire or even explode and the gas emissions are toxic and thus harmful to the operators of such a plant. The viscose fibers as such are on the other hand very good. We have therefore started a project where we try to produce more viscose fibers based on cellulose but we also try to reuse the current waste steams as much as possible both in the viscose plant and in the dissolving pulp mill. The first part of this study discussed the integration of a prehydrolysis kraft pulp mill and a viscose plant and this has already been published (Magnusson 2016). The current study can be considered as being the second case of integration of a pulp mill and a green viscose plant. Thus, we have studied the case where a sulphite pulp mill and a viscose plant are connected. The pulping process has been either a sodium or a magnesium sulphite dissolving pulp mill where the pH in the cook has been either 1,5 throughout the cook or initially 4,5 which has been reduced to 1,5 in the second part of the cook 14 Figure 1: A sulfite dissolving pulp mill and an integrated traditional viscose plant . In the pulping stage either sodium or magnesium is used and the pH in the first stage is either 4,5 /1,5 or just 1,5. A number of benefits can be achieved if a dissolving pulp mill and a viscose plant are connected and the most obvious are the following: The energy saving obtained as the pulp is not fully dried between the pulp mill and the viscose plant. It is naturally easier to reuse a waste stream if the pulp mill is using sodium as base instead of magnesium. If sodium is the base a conventional oxygen delignification stage with filtrate recycling can easily be included in the bleach plant. An oxygen stage based on MgO as alkali is an option for magnesium based sulphite mills but such a stage performs relatively poor if the temperature is unchanged. If the temperature is raised 20-30 oC the delignification will be OK but the selectivity measured as viscosity goes down significantly. Sulfuric acid is often needed in the bleach plant and in the spinning stage and sulfur rich gases in the pulp mill could be utilized for such production. The discharge streams contain high amounts of hemicellulose and lignin and these should naturally be taken care of. However, also when these components are separated the filtrate streams are interesting as water is needed for dilution and washing etc. Thus, the combined pulp mill and viscose plant will have a much lower pollution impact than if these were located independently from each other. Carbon disulfide is used in the viscose process but it is a chemical difficult to handle because of its poisonous properties and the risk for explosions. CS2 can be produced onsite based on carbon and elemental sulfur as raw material. CONCLUSIONS Integration of a dissolving pulp mill and a viscose plant has many benefits with respect to improved process economy and reduced pollution of the environment. For a sulfite pulp mill the best option is if the cation (the base) is sodium instead of magnesium. REFERENCES Magnusson, H., Kvarnlöf N., Henriksson G. and Germgård U. (2016). Integrating prehydrolysis kraft pulping of softwood and viscose fiber manufacturing. Appita (69) 3, 264-272. 15 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 1 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 1 22-23 September 2016 Molecular deformation and orientation in ionic liquid spun cellulose fibers Functional dense and porous nanofibrillated cellulose substrates 1 2 Paola Orsolini1,2, Carlo Antonini1, Thomas Geiger1, Tanja Zimmermann, Walter R. Caseri2. 3 Nandula D. Wanasekara , Anne Michud , Chenchen Zhu , Sameer Rahatekar4, Herbert Sixta5, Stephen J. Eichhorn6 1 2 College of Engineering, Maths and Physical Sciences, Harrison Building, North Park Road, University of Exeter, UK Department of Forest Products Technology, Aalto University, P.O. Box 16300, Vuorimiehentie 1, Espoo, FI-00076, Finland 3 Advanced Composites Centre for Innovation and Science (ACCIS), Aerospace Engineering, University of Bristol, Bristol, UK 1 2 Empa, Swiss Federal Laboratories for Materials Science and Technology, Applied Wood Materials, Dübendorf, Switzerland. [email protected] Eidgenössische Technische Hochschule (ETH),Multifunctional Materials, Zürich, Switzerland. Keywords: methyltrichlorosilane, superhydrophobicity nanofibrillated cellulose, oil remediation, ABSTRACT Keywords: Ionic Liquid, Cellulose, Molecular Deformation ABSTRACT Solubility of cellulose in Ionic liquid offers a sustainable alternative to traditional processing methods for fibers. The deformation micromechanics and structure-property relationships are not well understood on ionic liquid spun fibers. In this work, we have explored the molecular deformation and crystal orientation of cellulose fibers, produced from an ionic liquid solvent spinning system. The orientation of molecules relative to the long axis of the fiber was mapped using Raman spectroscopy by monitoring the change in intensity of a Raman band located at 1095 cm-1. Wide angle X-ray diffraction was used to understand the crystal orientation of fibers showing higher orientation of crystals for fibers with higher draw ratios. Tensile testing of these fibers disclosed that a significant increase of Young's modulus and tensile strength was observed when the fiber draw ratio is increased from 1 to 6. A crystalline chain slip model was used to predict the Hermans' orientation parameter values for each draw ratio and a good match between data and the model suggest dominant crystalline affine deformation along the longitudinal fiber axis. The findings of this work have lead to recommendations to improve the elastic moduli of the fibers further. In order to increase the mechanical properties of fibers, a reduction of chemical and physical impurities in the fibers and an increase in the total molecular and crystal orientation is essential. Another important factor in increasing the modulus is to minimize the skin-core differences that exist in the degree of preferred orientation of crystals (Gindl et al. 2006, Kong et al. 2012). En enhanced modulus may be achieved by a more uniform orientation of molecules and crystals in both skin and core of the fiber. In the last decades, nanofibrillated cellulose (NFC) has gained interest not only as reinforcing material in polymer composites, but also as building block for dense and porous substrates. Among the most promising applications in our laboratory, main efforts have been made to develop membranes and oil-sorbent foams to target applications such as water purification and oil-pollution remediation. In the present work, we characterized the porosity of dense membranes by means of different techniques (Fig. 1), such as mercury intrusion, gas adsorption and thermoporometry (Orsolini, Michen et al. 2015). Such membranes were produced by a traditional papermaking process from a water-based NFC suspension which led to a highly compact structure (porosity ~5%), thus their permeance was not competitive with commercial membranes. Therefore, we focused on enhancing the permeance by a templating approach based on the use of calcium carbonate nanoparticles. Thanks to this strategy, the permeance could be increased by one order of magnitude. We further worked on the chemical functionalization of the NFC substrates with methyltrichlorosilane to grow polysiloxane nanofibers on their surfaces (Fig. 2). In this case, the amphiphilic behaviour of cellulose was changed to foster oil-adsorption and water repellence at the same time. In this part of the study dense membranes, porous membranes and foams were modified to benefit from the combination of silane chemistry and different surface roughness to achieve superhydrophobicity and enhanced the oil-adsorption capacity. REFERENCES Gindl. W., Martinschitz. K.J., Boesecke, P., Keckes, J. (2006) Orientation of cellulose crystallites in regenerated cellulose fibres under tensile and bending loads. Cellulose, 13, 621–627. Kong, K., Deng, L., Kinloch, I. A., Young, R. J., Eichhorn, S. J. (2012) Production of carbon fibres from a pyrolysed and graphitised liquid crystalline cellulose fibre precursor. Journal of Material Science, 47, 5402–5410. 16 Figure 1: Characterization of cellulose substrates by means of different techniques. 17 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 1 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I Novel environmental friendly new method for crosslinking of Cellulose Nanocrystals (CNCs) via esterification T. Ben Shalom1, A. Rivkin1, T. Abitbol1, Y. Nevo1, S. Lapidot2, O. Shoseyov1 1 Figure 2: a) NFC foam, b) NFC porous membrane and c) Polysiloxane nanofilaments grown on a NFC membrane REFERENCES Orsolini, P., B. Michen, A. Huch, P. Tingaut, W. R. Caser and T. Zimmermann (2015). Characterization of Pores in Dense Nanopapers and Nanofibrillated Cellulose Membranes: A Critical Assessment of Established Methods. Acs Applied Materials & Interfaces, 46, 2588425897. The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew University of Jerusalem, Rehovot 76100, Israel 2 Melodea Ltd. The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew Universit y of Jerusalem, Rehovot 76100, Israel. [email protected] ABSTRACT Nanocrystalline cellulose (NCC) is grown under controlled conditions that lead to formation of high-purity single crystals, CNCs from sulfuric acid hydrolysis form stable suspensions in water due to repulsive interactions from charged groups grafted on during hydrolysis and exhibit interesting self-assembly, optical and mechanical properties that make them suited for a wide range of applications. Carboxylic acids were found to be good cellulose crosslinking agents, whereas the polycarboxylic acid 1,2,3,4butanetetracarboxylic acid (BTCA) was found to be one of the best performing polycarboxylic acids. Sodium hypophosphite (NaH2PO4) is a most effective catalyst for catalyzing a reaction with BTCA. This method serves the textile industry for crosslinking of cotton cellulose to improve anti-pilling, wrinkle recovery, antimicrobial, water repellent and flame retardant properties of the cotton fabric. In the current work BTCA and NaH2PO4 (SHP) are used to crosslink CNC. The combination of crosslinking system with CNC results unexpected new high performing material. CNC esterification with a polycarboxylic acid begins with the formation of a cyclic anhydride, followed by covalently binding to a hydroxyl group (-OH group) of the CNC, forming an ester bond. CNC cross-linked films were prepared by spreading the aqueous suspensions of CNC/BTCA/SHP onto flat glass followed by water evaporation under ambient conditions. We were interested in understanding the mechanical properties of films made by combining one of nature’s strongest materials, CNCs, with environmental friendly nontoxic crosslinking method, the mechanical tests used to evaluate the effect of BTCA/SHP cross linking on the material properties of CNC films. The Instron tests were in tensile mode, whereas the Instron testing shows the results for CNC/BTCA/SHP, and neat CNC films. Overall, the results highlight that the mechanical behavior of the films. The cross linked films displayed a significant increase in the average moduli and tensile stress and strain values at break, resulting in tougher films on average . The crosslinked CNC films were easier to handle since they were less brittle. In comparison to the other CNC films studied, CNC/BTCA/SHP films had higher average moduli and tensile stress and strain values at break 2to 4-fold compared to neat CNC. As describe above the crosslinked CNC films exhibited unexpected enhancement in the mechanical properties in comparison to regular CNC films and also appear to be more transparent that uncrosslinked films. The alignment of the NCC in the films was explored using polarized optical microscopy coupled with an image processing module that is able to confer the direction of sample alignment. The neat CNC films are 18 19 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I birefringent and show the typical fragmented, multi-domain order that is characteristic of CNC films prepared by water evaporation. In contrast, the CNC cross linked films appear uniformly birefringent and the polarized microscopy image processing technique interprets long-range nematic order. To the best of our knowledge, this is the first report of alignment induced in CNC by BTCA/SHP. Future research should combine disciplines from different fields of biology, materials engineering and polymers engineering in order to further improve and adjust the mechanical properties of such composites according to the required applications in the biomedical fields as well as other industrial fields such as sports, automotive, construction and more as bio-based replacement for synthetic materials. . A novel method to produce polymer nanolatexes by Pickering emulsification with modified cellulose nanocrystals (CNCs) Arthur Werner1, Gilles Sèbe1, Valérie Heroguez1, University of Bordeaux, ENSCBP, Laboratoire de Chimie des Polymères Organiques, Bordeaux, France. [email protected] 1 Keywords: Nanolatex, Pickering emulsion, Acetylated CNCs ABSTRACT Polymer nanolatexes are nanosized polymer materials with unique properties, which can find applications in a wide range of domains such as paint, films or rubbers. Their preparation is usually performed by miniemulsion polymerization, using chemical surfactants (Hu, Zhang and Yang) or inorganic Pickering stabilizing particles (Bon and Colver 2007), which are rarely sustainable and can be toxic. These synthetic procedures are also generally tricky and require harsh reaction conditions. In this context, we report a new simple strategy to synthesize surfactant-free nanolatexes, by Pickering emulsification with modified cellulose nanocrystals (CNCs) (Fig 1). The hydrophilic/hydrophobic balance at the CNCs surface was monitored by acetylation with vinyl acetate, to produce nanoparticles that can serve as Pickering surfactant for the stabilization of styrene-in-water emulsions. The controlled polymerization of the stabilized monomer droplets was subsequently achieved, leading to the production of nanolatex composed of polystyrene nanobeads in a relatively high yield. The impact of CNCs concentration, acetylation level and initiator concentration on the dimensions of the nanobeads produced will be particularly discussed. Figure 1: a) TEM microscopy of the nanobeads escaping from the Pickering droplets. b) TEM microscopy of the polystyrene nanolatex. REFERENCES X. Hu, J. Zhang, W. Yang, (2009), Preparation of transparent polystyrene nano-latexes by an UV-induced routine emulsion polymerization. Polymer, 50, 141–147 S. A. F. Bon and P. J. Colver, (2007) Pickering miniemulsion polymerization using laponite clay as a stabilizer, Langmuir, 23, 8316-8322 20 21 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I In situ synthesised NanoCellulose – Hydroxyapatite based composites for phenol and cobalt adsorption Cellulose degradation products as a raw material for PUR foams 1 1 Vijaykiran N. Narwade , Rajendra Khainar , Vanja Kokol 2 1 School of Physical Sciences, S.R.T.M. University, Nanded, Maharashtra, India. Sylwia Witek1, Paweł Parzuchowski2 , Mariusz Mamiński1 Warsaw University of Life Sciences – WULS, Faculty of Wood Technology, 159 Nowoursynowska St., 02-787 Warsaw, Poland. [email protected] 1 2 2 University of Maribor, Faculty of Mechanical Engineering, Maribor, Slovenia; [email protected] Warsaw University of Technology, Faculty of Chemistry, 3 Noakowskiego St., 00-664 Warsaw, Poland Keywords: Composite, Hydoxyapatite, NanoCellulose, Wastewater cleaning Keywords: agrowaste, cellulose degradation, foam, wood liquefaction ABSTRACT The present study deals with the in situ synthesis of Cellulose NanoFibrils (CNFs) and TEMPO oxidized CNFs with precursors of Hydroxyapatite (HAp) to nanocomposites, and their relevance for eradicating organic pollutant i.e. phenol and cobalt from the waste water. The prepared samples are characterized by X-ray diffraction and Fourier Transform Infrared spectroscopy reveals the formation of HAp. The surface and morphology characteristics of the native and CNF-HAp composites are verified by Scanning Electron Microscopy showing well growth occurred HAp platelets on the nanocellulose matrix and the porous nature of composites. The prepared samples were used to evaluate phenol and cobalt adsorption kinetics as a function of pH, and the maximum adsorption capacities were calculated from the kinetic models. Acknowledgements. The work was supported financially by the Erasmus Mundus project Euphrates (2013-2540/001-001-EMA2). ABSTRACT The environmental policy of the 21st century imposes the maximized utilization of the cellulosic raw materials. The approach regards agrowaste too. Malaysian and Indonesian oil palm (Elaeis guineensis) plantations generate huge amounts of waste trunk. The quantity is estimated on 5 million tonnes annualy. The feedstock is still unutilized and new pathways of its conversion are welcomed. The content of holocellulose and α-cellulose in the material is 73% and 33%, respectively. Thus, the purpose of this study was to investigate the possibility of use liquefied palm oil wood as polyols for the production of polyurethane foams. Application of palm wood for PUR production would be an opportunity for use readily available material at industrial scale. Liquefaction is an acid-catalyzed chemical degradation of cellulose in presence of phenol, glycols, glycerol or cyclic carbonates (Yamada and Ono, 1999). The solvolysis yields a mixture of cellulose and hemicelluloses degradation products that can be used as polyols for polyurethanes or building blocks for various types of polymers (Kunaver et al. 2010, Kobayashi et al. 2004) (Fig. 1). Thus, so-called “liquefied wood” can be a cellulose-derived resource of the components for PUR foams (Pan et al. 2012). Figure 1: Solvolysis of cellulose Wood of density 297±30 kg/m3 was ground and sorted. The fraction < 32 mm was used for further work up. The liquefaction procedure was as follow: 65 min at 150°C and 65 min at 180°C in a mixture of ethylene glycol/glycerol (1:1, vol/vol) containing 3%wt of sulfuric acid. Products of the liquefaction were diluted with dioxane/water (4:1, vol/vol), filtered off and concentrated. The determined hydroxyl value (LOH) of the polyol was 700 mg KOH/g. Molecular weight distribution (MALDI-TOF) of the liquefaction products was below 750 Da (Fig. 2) which proved a complete degradation of cellulosic material. 22 23 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I Surface chemistry of sonochemically-treated bacterial cellulose Dimitirios Tsalagkas1, Leena-Sisko Johansson2, Orlando J. Rojas2, Levente Csoka3 1 Inha University, Department of Mechanical Engineering, 21999 Incheon, South Korea. [email protected] 2 Figure 2: MALDI-TOF spectrum of the liquefaction products Aalto University, Department of Forest Products Technology, 16100 Espoo, Finland [email protected] 3 The liquefied wood products were used as a biopolyol for the preparation of polyurethane foams. Liquefied wood comprised 0% to 100% of the formulation in a mixture with polypropylene glycol (PPG). The isocyanate (PMDI) index was adjusted to 1.05. The following conclusions were withdrawn from the obtained results: 1. The approach allows to increase utilization of high-cellulose agrowaste in PUR foams manufacturing. 2. The content of the biopolyol exhibited the influence on the foaming start time that was shortened from 30 s to 10 s when biolpolyol amount increased from 0% to 100%. On the other hand, foam tack-free times were lengthened from 100 s to 540 s. 3. The density of foams was affected by the content of degraded cellulose products in a formulation (16–26 kg/m3 for 30% to 100% of liquefied wood). 4. Stability of the foams was comparable to those of the commercial PUR foams. Shrinkage of the sample after heating for 72 hrs at 80°C ranged from 1.8% to 6.6% and depended on the degraded cellulose products content (30%–100%). REFERENCES Kobayashi M., Asano T., Kajiyama M., Tomita B., (2004). Analysis on residua formation Turing Wood liquefaction with polyhydric alcohol. Journal of Wood Science, 50, 407-414. Kunaver, M., Medved, S., Čuk, N., Jasiukaityte, E., Poljanšek, I., Strnad, T., (2010). Application of liquefied wood as a new particle board adhesive system. Bioresource Technology, 101, 1361-1368. Pan, H., Zheng, Z., Hse, C.Y., (2012). Microwave-assisted liquefaction of wood with polyhydric alcohols and its application in preparation of polyurethane (PU) foams. European Journal of Wood and Wood Products, 70, 461-470. Yamada, T., Ono, H. (1999). Rapid liquefaction of lignocellulosic waste by using ethylene carbonate. Bioresource Technology, 70, 61-67. 24 University of West Hungary, Institute of Wood Based Products and Technologies, 9400 Sopron, Hungary [email protected] Keywords: microbial cellulose, XPS, ultrasound ABSTRACT Bacterial cellulose (BC) is a material relevant to several applications, including biomedical, nanocomposite and smart/electric systems. The surface properties of BC such as surface charge, chemical composition, reactivity and accessibility are strongly associated to the interfacial interactions of BC fibrils, their modification and performance. The production of BC as well as the factors which influence BC yield and its physicochemical properties have been investigated. The aim of this research is to examine the surface composition of a commercially available, pristine BC (from nata de coco) before and after sonochemical treatment of alkaline purified BC, through X-ray photoelectron spectroscopy (XPS). BC (PT Cocomas, Indonesia) was washed and soaked in pure water several times in order to remove citric acid and other components in the nata de coco syrup and blended, after which the material was oven dried at 50℃. A portion of the washed BC was further purified by alkaline treatment (0.01 M NaOH at 70℃ for 2 h under continuous stirring) blended and oven dried. Dry samples were redispersed (0.1% w/w), and ultrasonicated (cold water bath, 30 min, 25 W cm-2) and these BC dispersions were dried for a second time into nanostructural, self-assembled thin films. The XPS surface chemical analysis of the BC films was recorded using a Kratos Analytical AXIS ULTRA electron spectrometer with monochromatic A1 Kα irradiation at 100 W and under neutralization. Whatman cellulose filter paper, analysed with the samples, was used as a reference for pure cellulose. The relative atomic concentration and surface chemical groups determined by XPS are given in Table 1. Fig. 1 shows the typical wide-scan and high resolution spectra for C 1s, O 1s, and N 1s of the BC samples, together with cellulose reference. The O/C ratio (0.50) in both BC samples was much lower than the theoretical value for pure cellulose (0.83) and Whatman filter paper (0.68) or other BC values reported (Li et al. 2009, Pertile et al. 2010, Kurniawan et al. 2012). Differences on the amount of element components and O/C ratio could be related to the instrumental and production methods but also to the degree of contamination. Surprisingly, N amount was increased after the combination of alkaline purification and ultrasound treatment. According to the high resolution C 1s data, the elevated non-cellulosic C-C component indicate that the surface of the pristine and ultrasound-treated BC were not pure cellulosic. This result was expected since fibril surfaces of all aqueous cellulose samples become passivated during the drying process and the agglomeration of BC fibrils 25 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I (Österberg et al. 2013). Furthermore, increasing nitrogen together with diminishing C-C content in the purified sample suggest that the nitrogen observed, possibly of bacterial origin, was buried under the passivation layer and became more exposed the purification. Bacterial nanocellulose glycidyl methacrylate grafting. Preparation and perspective. Table 1: Elemental surface concentrations and relative abundance of carbon bonds of BC samples Surface elemental composition (%) Samples BC Ultra BC Whatman C 65.8 64.5 59.6 O 33.1 32 40.4 N 1.1 3.2 - Na 0.3 - Chiara Bongio, Andrea Bernardi, Marco Zarattini, Elena Vismara Politecnico di Milano, Dipartimento di Chimica Materiali e Ingegneria Chimica “G. Natta”, Italy. [email protected] Surface chemical groups (%) C-C 29 26.9 3.9 C-O 54.8 54.8 75.7 C=O 14 16.4 18.6 COO 2.3 1.9 1.8 Keywords: amoxicillin, bacterial nanocellulose, drug delivery, glycidyl methacrylate ABSTRACT Bacterial nanocellulose (BNC) was grafted with glycidyl methacrylate (GMA) affording BNC-GMA. Substitution degree (DS= GMA residue versus glucose unit) range in BNC-GMA is 0.6-3. Figures 1 and 2 show NMR CP MAS spectrum of BNC and BNCGMA, respectively. As GMA grafting forms a new C-C bond between cellulose and GMA and keeps OH cellulose groups unchanged, BNC-GMA maintains the BNC crystallinity, see the NMR spectra. GMA appendages enhances BNC capability to adsorb amoxicillin (A), as summarised in Table 1. GMA was further transformed to GMAOH by opening the epoxide group with water. BNC-GMAOH adsorbs amoxicillin (A) less than BNC-GMA, but more than BNC. It seems that the hydrophobic appendages GMA make BNC capable to include A. Nevertheless the GMA modified BNC can include A better than BNC. We can conclude that glycidyl methacrylate grafting opens the way to new modified BNC suitable to develop as drug delivery system. Figure 3 reports BNC-GMA SEM image. Figure 1: XPS wide spectra and high resolution C 1s, O 1s and N 1s spectra of BC samples Based on the results, BC impurities were successfully removed after the sonochemical treatment of alkaline purified samples. Additionally, their crystallinity index and thermal stability were increased, while surface charge was decreased. Further research on the wettability and the surface accessibility and reactivity of the available hydroxyl groups on the surface of these BC films will provide more useful information. Figure 1: BNC NMR. ACKNOWLEDGEMENTS This work is based upon a STSM Grant from COST Action FP1205 “Innovative applications of regenerated wood cellulose fibres”, supported by COST (European Cooperation in Science and Technology). This work made use of Aalto University Bioeconomy Facilities. REFERENCES Kurniawan, H., Laim JT. And Wang, MJ. (2012). Biofunctionalized bacterial cellulose membranes by cold plasmas. Cellulose, 19, 1975-1988. Li, J., Wan, Y., Li, L., Liang, H. and Wang, J. (2009). Preparation and characterization of 2,3-dialdehyde bacterial cellulose for potential biodegradable tissue engineering scaffolds. Materials Science and Engineering C, 29, 1635-1642. Pertile, RAN., Andrade, FK., Alves Jr, C. and Gama, M. (2010). Surface modification of bacterial cellulose by nitrogen-containing plasma for improved interaction with cells. Carbohydrate Polymers, 82, 692-698. Österberg, M., Peresin, MS., Johansson, LS. and Tammelin, T. (2013). Clean and reactive nanostructured cellulose surface. Cellulose, 20, 983-990. 26 27 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I Figure 2: BNC-GMA NMR. Preparing of nanoparticles from partly derivatized cellulose Kay Hettrich1, Bert Volkert1 1 Fraunhofer Institute of Applied Polymer Research, Department of Biopolymer, D-14548 Potsdam, Germany. [email protected] Keywords: cellulose derivative, etherification, nanoparticles, oxidation ABSTRACT Figure 3: BNC-GMA SEM. Novel nano-scaled cellulose particles have been prepared by high-pressure homogenizing of different pre-treated cellulose samples with Microfluidizer ™ processor (MF) in aqueous media. One possibility of pre-treatment is the preparation of partly derivatized cellulose. Initially cellulose derivatives with low degrees of substitution were prepared (DS > 0.5). Afterwards nano-cellulose was obtained by a subsequent high-pressure mechanical treatment in aqueous dispersion. Different etherification, esterification or oxidation reactions were used for the preparation of nanoparticles in principle. The properties of the different nanocellulose dispersion were investigated. In order to obtain information about cellulose particle sizes, UT and MF treated dispersions were characterized by means of static and dynamic light scattering (DLS), ultra-centrifugation and scanning electron microscopy (SEM), rheological measurements revealed the viscoelastic properties and gel-like structure of the materials as well as time- and shear-dependent effects like thixotropy and pseudoplasticity (structural viscosity). Table 1: BNC -GMA adsorption of amoxicillin (A) Nanocell. time (h) 0 24 BNC-GMA 48 52 0 BNC-GMAOH 24 48 BNC 24 A/ A A A mg /mg nano 0 3,72 4,27 2,53 0 1,32 0,46 0,4 In conjunction with potential applications film forming properties and temperature dependent behaviour (e.g. viscosity) of the materials were investigated. Selected samples of nano-cellulosic dispersions were dried via lyophilizsation, via spray drying, and solvent exchange. The dried products were characterized in terms of porosity (mercury porosimetry) and particle morphology (SEM). Re-dispersed samples were compared with starting dispersions by means of SEM, DLS and rheometry. REFERENCES Vismara, E., Zarattini, M., Bernardi, A., Nanni, D., Bertini, S., Freire, C. Allyl, glycidyl methacrylate and cyclodextrin-modified nanocelluloses. Preparation, characterisation and adsorption-release specific properties. Advanced Materials TechConnect Briefs 2016, Vol. 1 Chapter 6: Nano and Microfibrillated Cellulose. Pages 172-175 28 29 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I Perspective use of solubilised cellulose in microbial fuel cells (MFCs) The bacteria used in the MFC were isolated from cow gastrointestinal system that was reported to have electrogenic activity (Inoue et al. 2013, Zheng and Nirmalakhandan 2010). The catholyte solution was 100 mM K3Fe(CN)6 in phosphate buffer. The anode chamber was sealed with rubber stopper and the cathode chamber was in contact with air. Warsaw University of Life Sciences – WULS, Faculty of Wood Technology, 159 Nowoursynowska St., 02-787 Warsaw, Poland. [email protected] Keywords: bioenergy, cellulose solubilisation, MFC ABSTRACT The annual biosynthesis of cellulose in the environment has been estimated on 100 million tons. This way cellulose has become the most abundant terrestrial biopolymer in the world. Such plentiful source of carbon-rich biomass has a great potential of being an alternative substrate for energy production. For this reason converting waste cellulosic feedstock into energy has attracted great attention in recent years. Such process has been realized in microbial fuel cells (MFCs). MFC technologies represent the newest approach for generating clean energy. MFC is commonly known as bioelectrochemical system producing current rendered by the microorganism activity. From chemical point of view, MFC is electrochemical cell where microorganisms catalyze electrochemical reaction (oxidation or reduction). Typical MFC is built of two electrodes: anode and cathode placed in compartments separated by proton-exchanging membrane enabling flow of the current between electrodes. Microorganisms are placed in the anode compartment where they mediate in converting organic substrate into energy. As bacteria respire, they release electrons that are transferred from the anode to the cathode what creates electric current (Logan 2008). Cellulose, like most biopolymers, has high energetic content, but is water insoluble what makes it difficult substrate for energy-producing biosystems application. Naturally occurring cellulose has crystalline structure with small amounts of amorphous regions. The crystalline regions are resistant to bacterial enzymatic hydrolysis what eliminates it as a carbon source for energy production in MFC systems. The problem is also complicated by the secondary structure of cellulose e.g. monomer linkage, strands and microfibrils. In this work we proposed alkaline and thermal pretreatment (solubilisation) of cellulose before its application in MFC system. Fibrous cellulose (Sigma Aldrich) 740 mg was suspended in 20 mL of 2M NaOH solution and the mixture was shaken at room temperature. Next, the suspension was placed at –20°C temperature until frozen. The frozen suspension was thawed and ultrapure water was added to the sample, so that the final concentration of cellulose in 1.3M NaOH was 2%. Subsequently, the cellulose sample was suspended in NaOH/thiourea solution (1.5 M NaOH/0.65 M thiourea), and the mixture was shaken at room temperature. The suspension was stored at –20°C until frozen. After thawing, the cellulose sample was stirred to give a transparent cellulose solution (Sugano et al 2010). The solubilised cellulose was applied as a substrate in MFC system. The MFC was composed of 30 ml cathode and 30 ml anode chambers separated by agar bridge (10% agar, 10% NaCl). The anode and cathode were graphite electrodes. The anode solution was 50 mM phosphate buffer, 1% raw cellulose or 1% solubilised cellulose. 30 The maximum power density in MFC system obtained for raw cellulose as a substrate exceeded 18.5 mW/m2 which corresponded current density 173 mA/m2 (Fig. 1). The operation on the solubilised cellulose caused increase in current production to 400 mA/m2 and maximum power density 28 mW/m2. Apparently, solubilisation improved availability of cellulose to microorganisms and enzymes. Thus, it has been shown that cellulose-rich materials, when properly treated, may be involved in bioenergy domain and are useful substrates in biological systems for electrical power generation. 30 raw cellulose 25 power density [mW/m2] Renata Toczyłowska-Mamińska cellulose solubilized 20 15 10 5 0 0 100 200 300 400 500 600 700 current density [mA/m2] Figure 1: Polarization curves of raw and solubilised cellulose-fed MFCs. REFERENCES Inoue K., Ito T., Kawano Y., Iguchi A., Miyahara M., Suzuki Y., Watanabe K., (2013). Electricity generation from cattle manure slurry by cassette-electrode microbial fuel cells. Journal of Bioscience and Bioengineering, 116, 610–615. Logan B.E. (2008). Microbial fuel cells. Wiley&Sons Inc. Publication, Hoboken New Jersey Sugano Y., Vestergaard M., Yoshikava H., Saito M., Tamiya E., (2010). Direct electrochemical oxidation of cellulose: A cellulose-based fuel cell system. Electroanalysis, 22, 1688-1694. Zheng, X. and Nirmalakhandan, N. (2010) Cattle wastes as substrates for bioelectricity production via microbial fuel cells. Biotechnology Letters, 32, 1809–1814. 31 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I COST ACTIONPoster FP1205 BUDAPEST 22-23 September 2016 presentations I Spider silk-CBD-CNC composites: mechanism of assembly Production and properties of nanocrystalline cellulose suspensions and films Zvi Shtein1, Sigal Meirovitch1, Shaul Lapidot2, Oded Shoseyov1 1 The Robert H. Smith Institute of Plant Sciences and Genetics in Agriculture, Robert H. Smith Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, P.O. Box 2 12, Rehovot 76100, Israel Second Author Affiliation 2 Melodea Ltd. The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew University of Jerusalem, Rehovot 76100, Israel Sebestyén Nagy, Emília Csiszár Budapest University of Technology and Economics, Department of Physical Chemistry and Materials Science, H-1521 Budapest, Hungary. [email protected], [email protected] Keywords: sonication, haze, particle size, tensile properties Keywords: CNC, Spider silk, cellulose binding domain (CBD) ABSTRACT ABSTRACT Bio-inspired material systems are derived from different living organisms such as plants, arthropods and mammals. These biomaterial systems from nature are mostly present in the form of composites, with molecular-scale interactions optimized to direct functional features. Composite materials are macroscopic complexes of fibers or particles supported by a matrix. The combination of different materials in the composite may result in a variety of characteristics (e.g. flexibility, strength and toughness). CNCs are most commonly extracted by sulfuric acid hydrolysis of native cellulose. CNCs from sulfuric acid hydrolysis form stable suspensions in water due to repulsive interactions from charged groups grafted on during hydrolysis and exhibit interesting self-assembly, optical and mechanical properties that make them suited for a wide range of applications. Spider silk proteins form intrinsic composites dictated from their unique molecular structure that combine highly crystalline domains embedded in amorphous domains resulting in fibers that combine strength and elasticity. The fabrication of cellulose-spider silk bio-nanocomposites comprised of CNC and recombinant spider silk protein fused to a cellulose binding domain (CBD) is described. Silk-CBD self-assembled to form micro-fibers and successfully bound cellulose forming composite materials. Silk-CBD-CNC composites sponges and films shows changes in material alignment and internal structure with the addition of silk-CBD. . In this research cellulose nanocrystals (CNC) were prepared from bleached cotton fibres with sulphuric acid hydrolysis. After hydrolysis, low frequency ultrasound was applied varying the duration of sonication to study how the length of sonication influences the properties of CNC suspensions and those of the films prepared subsequently from the suspensions. Changes in size of particles were followed by lased diffraction analysis and transmission electron microscopy. For determining the surface charge of CNC, zeta potential was measured. Stability of the suspensions was characterized by the optical haze, which measures the percent of transmitted light that diffusely scatters. The films prepared from the suspensions were tested by measuring the haze, oxygen transmission rate, tensile and thermal properties (Csiszar et al. 2016). Laser diffraction analysis and transmission electron microscopy proved that the sonication of CNC suspensions not only disintegrated the large CNC aggregates (Dv50 14.7 μm) to individual nanowhiskers with an average length and width of 171 ± 57 and 17 ± 4 nm, respectively, but also degraded the nanocrystals and yielded shorter and thinner particles (118 ± 45 and 13 ± nm, respectively) at 10-min sonication. The ultrasound-assisted disintegration to nano-sized cellulose whiskers decreased the optical haze of suspensions from 98.4 to 52.8 % with increasing the time from 0 to 10 min, respectively. Sonication of the suspensions significantly contributed to the preparation of films with low haze (high transparency) and excellent tensile properties. With the increasing duration of sonication, the haze decreased (from 73.3 % to 22.2 %) and the tensile strength rose (by 8 - 57 %) gradually. Irrespectively of sonication, however, all films had an outstanding oxygen transmission rate in a range of 5.5 - 6.9 cm3/m2·day and a poor thermal stability. The best quality film with an averaged thickness of 48 μm was obtained after 10 min of sonication and could be characterized by a haze index of 22.2 %; a tensile strength of 32.9 MPa; an elongation of 2.1 %; an oxygen transmission rate of 6.7 cm3/m2·day and a Tonset of 203 °C. REFERENCE Csiszar, E., Kalic, P., Kobol, A. and Ferreira, E.P. (2016). The effect of low frequency ultrasound on the production and properties of nanocrystalline cellulose suspensions and films. Ultrasonics & Sonochemistry, 31, 473-480. 32 33 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 2 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 2 22-23 September 2016 Electrospun Nanofibres For Bio-Inspired Composite Materials and Innovative Industrial Applications Nanocellulose to Taylor the Barrier Performance of Electrospun Biopolyester Coatings and Layers for Food Packaging Applications S.J. Eichhorn College of Engineering, Maths & Physical Sciences, University of Exeter, Exeter, Devon, EX4 4QF, UK. [email protected]. Keywords: Electrospinning, nanofibres, composites ABSTRACT This talk will focus on both core understanding of the elecrospinning process and our ability to control the properties of the fibres and also the applications of nanofibres produced. Starting from fundamental models of the stochastic geometry of fibrous networks it will be shown how a control of the fibre diameter alone can be used to tailor pore sizes of networks. This can then be used to control the ingrowth of cells into networks, the use of networks in composite materials and the functionality of electrospun networks in a diverse range of applications. Following on from this it will be shown that cellulose acetate, a readily spinnable polymer, can be used as the basis for forming carbon fibres for electrocapacitive devices. Near field electrospinning will be introduced as a means for patterning fibres and finally the use of template assisted processes to make tuneable wetting surfaces, that mimic biological structures, will be reported. 34 A. Cherpinski1, L. Cabedo2, and J.M. Lagaron1 1 Novel Materials and Nanotechnology Group, IATA-CSIC, Av. Agustin Escardino 7, Paterna 46980 (Valencia), Spain. [email protected] ESID, University Jaume I, Castellón, Spain 2 Keywords: Nanocellulose, Electrospinning, Barrier paper, Food packaging ABSTRACT Electrospinning has emerged as a versatile plastic processing method to produce nanostructured materials such as nanocomposites and nanolayers for coating applications of paper and plastic packaging. Thanks to recent innovations in the scaling up of this technology, industrial applications are making their way forward and may soon become affordable for specialty applications such as barrier and active food packaging. This presentation shows recent results where nanocellulose was used as a filler to reinforce the barrier performance of electrospun biopolyesters such as polyhydroxyalcanoates to be used as paper and plastic coatings. The effect of different processing parameters and material combinations in mono and multilayer forms on the morphology, thermal, barrier and mechanical performance will be presented here. 35 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 2 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 2 22-23 September 2016 Heterogeneous Silanization of Cellulose Nanofibers with 3Aminopropyl triethoxysilane Cellulose in horticultural applications Eduardo Robles, Jalel Labidi 1 1Biorefinery Processes Research Group, Chemical & Environmental Engineering Department, University of the Basque Country UPV/EHU, Plaza Europa 1. 20018. Donostia-San Sebastian, Spain. [email protected] Keywords: aminopropyltrietoxysilane, cellulose nanofibers, silanization, ABSTRACT Abstract The surface modification of cellulose nanofibers with 3-Aminopropyl triethoxysilane by preserving cellulose structure and main properties was investigated. The effect of reaction conditions, such as time and solvent types on the extent of the silanization and fiber properties was evaluated by X-ray diffraction, thermogravimetry, 13C Nuclear Magnetic Resonance and electronic microscopy. Surface modification with organosilanes has been proved to be a good method to render nanocrystalline surface hydrophobicity, giving stability to the nanocrystals (Goussé et al., 2004). Silane chains can improve matrix-filler interactions either as suspension in organic solvents or added as bulk into the polymeric matrix (Xu et al., 2012; Raquez et al., 2012) by serving as a coupling agent between the cellulosic filler and the polymeric matrix. Cellulose nanofibers were modified with 3-Aminopropyl triethoxysilane (ATS) solution inside a plastic beaker to avoid ATS reactions with glass surface. Neat silane relation to cellulose nanofibers was 1:1, 2.5:1 and 5:1. ATS solution was first diluted in ethanol, ethanol-water (50/50) or water; pH was neutralized by dribbling acetic acid with constant stirring, once pH was neutral and stable, CNF were dispersed in ethanol, ethanol-water (50/50) or water at approximately 3 wt% and added to their corresponding silane solution. The mixture was stirred with a Silent crusher homogenizer at 1500 rpm during 5 min and left at room temperature for another 45 min. The slurry was vacuum-filtered to stabilize the cellulose content and kept at 10 wt% in the form of gel. For solid-state analysis the gel was oven cured until no humidity was left forming thin films. Victor Kisonen Bio-Co / EIC Ltd., Turku, Finland [email protected] Keywords: Biodegradable, cellulose, horticulture, gardening, natural fibre ABSTRACT For being biodegradable, bio-based and abundant, the cellulose fibre well fits into the sustainable gardening concept and the value-addition of cellulose can be considerable. Natural fibre reinforced biodegradable composites has been a considerable area of interest of industry (Mittal 2011). The green image increase the value of the brand and the product. Here are some examples of lignocellulosic horticultural applications in a market: cellulose derivative coatings in fertilisers and seeds, containers, hanging baskets, fabrics for plant root systems and weed isolation just to name few. For instance, lignocellulosic materials have been used to prepare biodegradable and nutritive pots for the vegetable seedlings (Nechita at al, 2010). This technology does not produce problematic plastic waste either. Inspired by these renewable material trends, we are going to develop biodegradable and bio-based horticultural applications for the use of plant nurseries, gardening retail sales and end-users. REFERENCES Nechita, P., Dobrin, E., Ciolocu, F., Bobu E., (2010). The biodegradability and nutrititive pots for vegetable planting based on lignocellulose composite material. Bio-Resources, 5, 1102-1113. Mittal, V. (2011). Bio-nanocomposites: future high-value material. In Nanocomposites with Biodegradable Polymers, Synthesis, Properties and Future Perspectives. Oxford University Press. REFERENCES Goussé C., Chanzy H., Cerrada M.L., Fleury E. (2004). Suface silylation of cellulose microfibrils: preparation and rheological properties, Polymer, 45, 1569-1575. Xu S.H., Gu J., Luo Y. F., Jia D. M. (2012). Effects of partial replacement of silica with surface modified nanocrystalline cellulose on properties of natural rubber nanocomposites, Express Polymer Letters Vol. 6, No. 1, 14-25. Raquez J. M., Murena Y., Goffin A. L., Habibi Y., Ruelle B., DeBuyl F., Dubois P., (2012). Surface modification of cellulose nanocrystals and their use as nanoreinfocers into polylactide: A sustainably-integrated approach, Composites Science and Technology, 72 544-549. 36 37 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 Cellulose nanofibers from industrial residues and their use in composite materials Herrera N, Roch H, Salaberria A M, Pino M A, Labidi J, Fernandes SCM, Radic D, Leiva A, Oksman K. (2016) Functionalized blown films of plasticized polylactic/chitin nanocomposite: preparation and characterization, Materials Design 92 846-852. Kristiina Oksman1,2 Luleå University of Technology, Division of Materials Science, SE-97187 Luleå, Sweden 1 [email protected] 2 University of Oulu, Fiber and Particle Engineering, Oulu, Finland Keywords: Applications, cellulose nanofibers, energy consumption, grinding process, nanocomposites processing, spinning, foaming, extrusion. ABSTRACT The presentation will introduce the audiences on production of cellulose nanofibers and nanocomposites, also their properties and some possible applications will be discussed. Cellulose nanocomposites have been very popular research subject during the last 15 years and many studies have been made on the development of these materials. Nanocelluloses can be prepared using mechanical and chemical methods. We are working with Masuko ultrafine grinding process and separation of industrial residues to nanosize cellulose and focussing on energy consumption and yield. The viscosity, optical microscopy images and mechanical properties are usually evaluated to follow the fibrillation process. X-ray diffraction (XRD) and Raman spectroscopy can be used to reveal that the materials are isolated without affecting their crystallinity. We have shown that a residue from carrot juice process is very easily bleached and consumes less energy during grinding process compared with common pulp. Moreover, dried nanofiber networks from carrot showed high mechanical properties, with an average modulus and strength of 12.9 GPa and 210 MPa respectively, thus indicating a homogeneous nanosize distribution. We believe that residues such as carrot have great potential for the industrial production of cellulose nanofibers because of the processing efficiency combined with low raw material cost. (Siqueira et al 2016, Berglund et al 2016) Processing methods such as foaming, solvent casting, resin impregnation, fiber spinning and extrusion of cellulose nanocomposites are currently of great interest and will be discussed. Addition of nanocellulose into the polymer matrix do not only improve the mechanical properties of the composite but can add new functionalities for the polymer but one of the difficulties, when producing cellulose-based nanocomposites, is to disperse the nanocellulose in the polymer matrix without degradation the polymer or the nanocellulose. Pros and cons are as well as future application are shown. (Aitomäki et al 2016, Herrera et al 2016, Hooshmand et al 2015, Oksman et al 2016, Zhou et al 2016, Siqueira et al 2016) Hooshmand S, Aitomäki Y, Norberg N, Mathew AP and Oksman K. (2015) Dry spun single filament fibers using only cellulose nanofibers from bio-residue, ACS Applied Materials and Interfaces 7 (23) 13022-13028. Oksman K, Aitomäki Y, Mathew AP, Siqueira G, Zhou Q, Butylina S, Tanpichai S, Zhou X, Hooshmand S. (2016) Review of the recent developments in cellulose nanocomposite processing, Composites part A 83 2-18. Siqueira G, Tadokoro S K, Mathew AP, Oksman K, (2016) Re-dispersible carrot nanofibers with high mechanical properties separated from juice residue, Comp Sci Technol 12349-56. Zhou X, Sethi J, Berglund L, Aitomäki Y, Frisk N, Sain MM, Oksman K. (2016) Dispersion and reinforcing effect of carrot nanofibers on biopolyurethane foams. Materials Design 110 526-531 REFERENCES Berglund L, Noël M, Aitomäki Y, Öman T, Oksman K. (2016) Production potential of cellulose nanofibers from industrial residues: efficiency and nanofiber characteristics, Ind Crops Prod 92, 84-92. 38 39 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 Hydrophobic nanocellulose-based aerogels for selective oil removal: an effective and simple method shows the evolution of the contact angle as the amount of AKD was increased for the three types of CNF selected. As it can be seen, the water contact angle was increased as the amount of AKD was too. Apparently, the use of the obtained aerogels shows a strong and environmentally friendly alternative for oil removal in the high seas. Quim Tarrés, Helena Oliver-Ortega, Miquel Llop, M. Àngels Pèlach, Marc Delgado-Aguilar, Pere Mutjé University of Girona, LEPAMAP research group, C/ Maria Aurèlia Capmany, 61, Girona (17003), Spain. [email protected] Keywords: aerogels, alkyl ketene dimer, cellulose nanofibers, oil removal ABSTRACT Nowadays, several methods are being used such as the collection of the oil on water surface (taking advantage of their different densities), dispersing oil in water promoting its natural degradation or in situ burning (Korhonen et al. 2011). Often, depending on the sensitiveness of the area, unfortunately the best option is to watch and wait for natural attenuation. None of the abovementioned methodologies seem to be quite efficient or environment-friendly. Many efforts have been performed to overcome this situation, such as depositing sawdust on water-oil mix surface with the purpose of removing the hydrophobic component. However, sawdust also absorbs water, which makes quite difficult its reuse (Nordvik et al. 1996). Cellulose nanofibers (CNF) have become one of the main topics of research for cellulose and polymer scientists and technicians. Aerogels made of CNF are a product of interest due to their lightweight, great specific surface and, thus, their huge porosity. Even they have been considered in the colloquial jargon as “solid smoke”. Moreover, aerogels made of CNF present great mechanical properties (Zhang et al. 2014, Ayadi et al. 2016), fact that confers them a good dimensional stability. CNF, in its native form, have a huge hydrophilic character (even greater than the abovementioned sawdust), what would make also difficult their use for oil removal. In this sense, chemical modification of CNF is also in a growing stage, mainly focused on the hydrophobization of their surface (Korhonen et al. 2011). There is some literature available where CNF are modified through silanation (Aulin et al. 2010) techniques and acetylation. The main drawback of these methods is the use of organic solvents, which at first sight, makes difficult their implementation at large scale mainly due to the strict safety regulations that these products force to adopt. In this sense, aerogels made of cellulose nanofibers from bleached kraft hardwood pulp will be developed by three well differentiated methodologies: TEMPO-mediated oxidation (Saito et al. 2007), enzymatic hydrolysis (Tarrés et al. 2016) and mechanical methods (Delgado-Aguilar et al. 2015). In addition, before preparing the aerogels, the obtained CNF will be properly modified by the addition of AKD, ranging the dosage between 0 to 10% and they will be submitted to some static and dynamic tests in order to determine the feasibility of using them as selective oil removers, as well as their capability to be used more than once (recycling tests). The visual aspect of the obtained aerogels was similar regardless the type of CNF used, as well as the added amount of AKD. Those aerogels modified with AKD presented, at first sight, a high water contact angle, which was quantified during aerogels characterization for each type of CNF and each modification degree. The water drops behaviour on aerogels surface can be observed in Fig. 1. On the other hand, Fig.1 also 40 Figure 1: Evolution of the contact angle as the amount of AKD is increased REFERENCES Aulin, C., Netrval, J., Wågberg, L. and Lindström, T. (2010). Aerogels from nanofibrillated cellulose with tunable oleophobicity. Soft Matter, 6(14), 3298-3305. Ayadi, F., Martín-García, B., Colombo, M., Polovitsyn, A., Scarpellini, A., Ceseracciu, L., Moreels, I. and Athanassiou, A. (2016). Mechanically flexible and optically transparent three-dimensional nanofibrous amorphous aerocellulose. Carbohydrate Polymers, Delgado-Aguilar, M., Tovar, I. G., Tarrés, Q., Alcalá, M., Pèlach, M. À. and Mutjé, P. (2015). Approaching a Low-Cost Production of Cellulose Nanofibers for Papermaking Applications. BioResources, 10(3), 5345-5355. Korhonen, J. T., Kettunen, M., Ras, R. H. and Ikkala, O. (2011). Hydrophobic nanocellulose aerogels as floating, sustainable, reusable, and recyclable oil absorbents. ACS applied materials & interfaces, 3(6), 1813-1816. Nordvik, A. B., Simmons, J. L., Bitting, K. R., Lewis, A. and Strøm-Kristiansen, T. (1996). Oil and water separation in marine oil spill clean-up operations. Spill Science & Technology Bulletin, 3(3), 107-122. Saito, T., Kimura, S., Nishiyama, Y. and Isogai, A. (2007). Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules, 8(8), 2485-2491. Tarrés, Q., Saguer, E., Pèlach, M. A., Alcalà, M., Delgado-Aguilar, M. and Mutjé, P. (2016). The feasibility of incorporating cellulose micro/nanofibers in papermaking processes: the relevance of enzymatic hydrolysis. Cellulose, 23(2), 1433-1445. hang, ., Sèbe, G., Rentsch, D., Zimmermann, T. and Tingaut, P. (2014). Ultralightweight and flexible silylated nanocellulose sponges for the selective removal of oil from water. Chemistry of Materials, 26(8), 2659-2668. 41 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 Preliminary results of the application of carboxymethylated cellulose as a reinforcing agent in papermaking Helena Oliver-Ortega1, Quim Tarrés1, Maria Àngels Pèlach1, Manel Alcalà2, Marc Delgado-Aguilar1, Pere Mutjé1. Table 1: Preliminary results in length rupture, tensile index and Schopper-Riegler degree of CMC addition in virgin fibres with a mechanical beating and in recycled fibres. BL (m)* Tensile index (N·m/g) * BL at pope (m)** 7,582 74.3 10,737 3,670 6,640 1 University of Girona, Group LEPAMAP, Department of Chemical Engineering, C/M. Aurèlia Capmany, nº61, 17003 Girona, Spain. [email protected] 2 University of Girona, Design, Development and Product Innovation, Dpt. of Organization, Business Management and Product Design, C/M. Aurèlia Capmany, nº61, 17003 Girona, Spain Keywords: Carboxymethylated Cellulose (CMC), Papermaking, Recycled Fibres, Sustanability. ABSTRACT Today, one of the main problems of papermaking industry is, as professor Martin Hubbe reported in a recent review, that “paper production requires large amounts of cellulosic fibre, whereas the world’s forested lands and croplands have a finite capacity to supply such resources” (Hubbe, 2014). In order to reduce this dependence from virgin fibres, the use of recycled fibres is being considerably increased. Actually, the 80% of the fibers used for paper production in Spain come from recovered papers. However, during paper recycling, fibers experience mechanical properties losses due to shear and friction forces, as well as hornification phenomena. In order to successfully recover the original paper properties, papermakers usually include mechanical refining in their paper production processes; nonetheless, it is well known that mechanical refining causes permanent and irreversible structural damages to fibers which considerably reduces fibers’ lifespan (Delgado-Aguilar, Tarrés, Pèlach, Mutjé, & Fullana-i-Palmer, 2015). In this sense, chemical-based strategies are gaining importance in papermaking research due to their lower side-effects on paper slurries. Among them, cellulose nanofibers as a reinforcing agent deserve special attention (Delgado-aguilar, González, Tarrés, Alcalà, & Pèlach, 2015; Tarrés et al., 2016). However, the efficiency of the cellulose nanofibres is reduced when they are used in mechanically refined fibres and also with recycled fibres. Another alternative is the use of carboxymethylated cellulose (CMC). While CMC is currently used in papermaking industries, it is usually as an ionic agent to control the high conductivity of the water, not for mechanical properties of paper enhancement. Some previous works showed significant increments in the mechanical propertites of the papers by the addition of CMC (Aarne, Kontturi, & Laine, 2012; Fras Zemljic, Stenius, Laine, & Stana-Kleinschek, 2008), although the reinforcing mechanism of CMC is still being investigated (Ankerfors, Duker, & Lindström, 2013). LEPAMAP group (University of Girona, Spain) has recently started to study the use of CMC as a reinforcing agent in papermaking. The addition of a moderate amount in two different fibres (virgin hardwood fibres and recycled fibres from newspapers and magazines) has shown really optimistic results (Table 1). The results shown above induce to consider the use of CMC as an alternative reinforcing agent in papermaking processes, leading the obtained papers to be used for high-performance applications or to implement several environmental friendly strategies such as reducing basis weights of papers or further increasing the amount of mineral fillers (i.e. PCC). 42 Virgin fibres + mechanical refining Virgin fibres + mechanical refining + CMC Recycled fibres Recycled fibres + CMC ᵒSR ΔBL (%) 10,614 32 - 105.3 15,032 37 41.6 36.0 65.1 5,138 9,296 40 60 80.9 BL: breaking length *Isotropic sheet former **An anisotropy ratio of 1.4 has been applied (Delgado-Aguilar, Tarrés, Puig, et al., 2015) REFERENCES Aarne, N., Kontturi, E., & Laine, J. (2012). Carboxymethyl cellulose on a fiber substrate: The interactions with cationic polyelectrolytes. Cellulose, 19(6), 2217– 2231. http://doi.org/10.1007/s10570-012-9793-2 Ankerfors, M., Duker, E., & Lindström, T. (2013). Topo-chemical modification of fibres by grafting of carboxymethyl cellulose in pilot scale. Nordic Pulp and Paper Research Journal, 28(1), 6–14. Delgado-aguilar, M., González, I., Tarrés, Q., Alcalà, M., & Pèlach, M. À. (2015). Approaching a Low-Cost Production of Cellulose Nanofibers for Papermaking Applications, 10(3), 5345–5355. Delgado-Aguilar, M., Tarrés, Q., Pèlach, M. A., Mutjé, P., & Fullana-i-Palmer, P. (2015). Are Cellulose Nanofibers a Solution for a More Circular Economy of Paper Products? Environmental Science and Technology, 49(20), 12206–12213. Delgado-Aguilar, M., Tarrés, Q., Puig, J., Boufi, S., Blanco, A., & Mutjé, P. (2015). Enzymatic Refining and Cellulose Nanofiber Addition in Papermaking Processes from Recycled and Deinked. BioResources, 4, 5730–5743. Fras Zemljic, L., Stenius, P., Laine, J., & Stana-Kleinschek, K. (2008). Topochemical modification of cotton fibres with carboxymethyl cellulose. Cellulose, 15(2), 315– 321. http://doi.org/10.1007/s10570-007-9175-3 Hubbe, M. A. (2014). Prospects for maintaining strength of paper and paperboard products while using less forest resources: A review. BioResources, 9(1), 1634– 1763. Tarrés, Q., Saguer, E., Pèlach, M. A., Alcalà, M., Delgado-Aguilar, M., & Mutjé, P. (2016). The feasibility of incorporating cellulose micro/nanofibers in papermaking processes: the relevance of enzymatic hydrolysis. Cellulose. http://doi.org/10.1007/s10570-016-0889-y 43 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 COST ACTION FP1205 SESSION BUDAPEST 3 22-23 September 2016 Relevance of retention systems when using cellulose nanofibers as strength additives in papermaking drained water on real time. Solids retention was also measured. Z-potential was measured in a ZetaPlus unit from Brookhaven Instruments (Holtsville, USA). Handsheets were prepared in a normalized (ISO 5269/2, DIN 54 358) sheet former Rapid-Köthen from PTI (Vorchdorf, Austria). These handsheets were conditioned in a weather chamber at 25 ºC and 50% humidity for 24 h before physical and mechanical tests were performed by using an AUTOLINE 300 from Lorentzen & Wettre (Stockholm, Sweden). The quality of the sheets formation was measured in a Beta formation tester from Ambertec (Espoo Finland). Noemi Merayo, Ana Balea, Elena de la Fuente, Ángeles Blanco, Carlos Negro 1 Complutense University of Madrid, Department of Chemical Engineering, Avda. Complutense s/n 28040 Madrid, Spain. [email protected] Keywords: cellulose nanofibers, drainage process, papermaking, paper strength, retention systems. ABSTRACT Cellulose nanofibers (CNF) have been successfully applied to increase paper strength (Balea et al. 2016a; Gonzalez et al. 2012; Petroudy et al. 2014). Moreover, CNF can reduce linting tendency during printing (Balea et al. 2016b) and provide especial properties to the paper, such as low porosity (Eriksen et al. 2008) or smoothness (Osong et al. 2016). CNF retention in the paper web is an important issue to consider, which is join to dewatering difficulties, and this is one of the important drawbacks for the implementation of CNF at industrial scale (Osong et al. 2016). During papermaking, retention systems are commonly used to assure retention of fines and fillers during the drainage step. In the case of CNF, a retention agent is also used, being cationic starch very common. In this research, several retention systems have been used in combination with CNF trying to avoid dewatering difficulties, but favouring CNF retention. Pulp was prepared through disintegration of 20 g of dry 100% recovered paper (60% old newspaper and 40% old magazine without inks) by using a Messmer pulp disintegrator (Mavis Engineering Ltd, London) at 180000 revolutions and 1 wt% consistency. CNF was obtained from never dried refined Eucalyptus globulus ECF bleached kraft pulp (EBK), with a Canadian Standard Freeness (CSF) of 540.8 mL, produced by Torraspapel S.A. in Zaragoza, Spain. Nanofibrillated material was obtained by TEMPO mediated oxidation, by using 5 mmol of NaClO per gram of EBK pulp (Saito et al. 2007), cleaning process through several cycles of dilution and filtration and six steps of homogenization at 600 bar in a laboratory homogenizer PANDA PLUS 2000 manufactured by GEA Niro Soavi (Parma, Italy). Five different retention systems (RS) were assessed in this study: (1) C-PAM formed by low molecular weight coagulant and high molecular weight polyacrylamide (PAM) (NALCO, Naperville, USA). (2) C-PAM-B formed by high molecular weight coagulant, high molecular weight PAM and hydrated bentonite clay (BASF, Ludwigshafen, Germany). (3) Chitosan (CH) of low molecular weight (PANREAC, Barcelona, Spain). (4) Cationic starch (CS) with degree of substitution of 0.02-0.17 (SOLAM, Emlichheim, Germany) (5) Polyvinylamine (PVA) of high molecular weight (BASF, Ludwigshafen, Germany). Results obtained in this research show that addition of CNF not always implies difficulties during the drainage process because behaviour during dranage depends strongly on the RS used. Moreover, CNF could contribute to solve the contradiction between the improvement in drainage rate and the improvement in sheet formation and mechanical properties. The use of CH as RS resulted in sheets with the highest values of TI, these values increased by using CNF. The use of 1% CNF is enough to revert the effect of using the C-PAM-B RS on the TI without affecting the drainage rate. Although the use of CNF and low doses of CS improves the TI of the paper, when the dose of CS used is that required to increase drainage rate, the high interaction between CS and CNF reduces the TI of the sheet. REFERENCES Balea, A., Blanco, A., Merayo, N. and Negro, C. (2016b). Effect of nanofibrillated cellulose to reduce linting on high filler-loaded recycled papers. Appita Journal, 69, 148-156. Balea, A., Merayo, N., Fuente, E., Delgado-Aguilar, M., Mutje, P., Blanco, A. and Negro, C. (2016a). Valorization of corn stalk by the production of cellulose nanofibers to improve recycled paper properties. Bioresources, 11, 3416-3431. Eriksen, O., Syverud, K. and Gregersen, O. (2008). The use of microfibrillated cellulose produced from kraft pulp as strength enhancer in TMP paper. Nordic Pulp and Paper Research Journal, 23, 299-304. González, I., Boufi, S., Pèlach, M.A., Alcalà, M., Vilaseca, F. and Mutjé, P. (2012). Nanofibrillated cellulose as paper additive in eucalyptus pulps. BioResources, 7, 51675180. Osong, S.H., Norgren, S. and Engstrand, P. (2016). Processing of wood-based microfibrillated cellulose and nanofibrillated cellulose, and applications relating to papermaking: a review. Cellulose, 23, 93–123. Petroudy, S.R.D., Syverud, K., Chinga-Carrasco, G., Ghasemain, A. and Resalati, H. (2014). Effects of bagasse microfibrillated cellulose and cationic polyacrylamide on key properties of bagasse paper. Carbohydrate Polymers, 99, 311-318. Saito, T., Kimura, S., Nishiyama, Y. and Isogai, A. (2007). Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromolecules, 8, 2485-2491. Drainage measurements were performed in a MütekTM DFR-05 from BTG Instruments (Säffle, Sweden), which provides drainage curves of the pulp when it is drained by gravity through 250 mesh. The program was monitoring and recording the weight of the 44 45 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II Synthesis and characterisation of nanocellulose aerogels for the elaboration of innovative biosourced bone substitutes. 100% recycled paper packaging materials: processing, properties and potential application Benjamin Dhuiège1, Laurent Plawinski,2 Marie-Christine Durrieu,2 Gilles Sèbe1,3 Laura Vikele, Linda Rozenberga, Inese Sable, Marite Skute, Linda Vecbiskena, Uldis Grinfelds, Juris Zoldners, Anrijs Verovkins, Rita Treimane 1 CNRS, LCPO, UMR 5629, F-33607 Pessac, France 2 CNRS, CBMN, UMR 5248, F-33607, Pessac, France Latvian State Institute of Wood Chemistry, 27 Dzerbenes Street, Riga, Latvia, LV-1006. [email protected] 3 University of Bordeaux, LCPO, UMR 5629, F-33607, Pessac, France Keywords: chitosan, moulded fibre, packaging, recycled paper [email protected] ABSTRACT Keywords: nanocellulose aerogels, biosourced scaffolds, innovative bone substitute ABSTRACT Nanofibrillated cellulose (NFC) is a nanomaterial composed of long, flexible and interconnected cellulose nanofibers, which can be produced by mechanical disintegration of cellulose substrates such as microcrystalline cellulose, paper or pulp. Because of its biocompatibility, excellent mechanical properties and renewability, this nanocellulose is increasingly considered as nanoscale building block for the elaboration of innovative materials, including biomedical materials (Tingaut et al. 2012, Lin and Dufresne 2014). In particular, NFC has the potential to serve as tissue bioscaffold by providing a cell-friendly environment to encourage the attachment and proliferation of cells (Lin and Dufresne 2014). In a recent work, we showed that flexible and ultralightweight nanocellulose aerogels with tunable properties could be prepared by a simple silylation method in water with alkoxysilanes (Zhang et al. 2014). Therefore, here we report on the synthesis of silylated NFC aerogels to be used as biosourced scaffold for the regeneration of bone tissues. Various silylated aerogels with different surface properties were synthesized in different conditions and characterized with regards to their chemistry, morphology, thermal stability and mechanical properties. The impact of the aerogels properties on the adhesion and the differentiation of Human mesenchymal stem cells will be later investigated in view of a potential application as bone substitute material. Tingaut, P., Zimmermann, T. and Sebe, G. (2012) Cellulose nanocrystals and microfibrillated cellulose as building blocks for the design of hierarchical functional materials. Journal of Materials Chemistry, 22, 20105-20111. Lin, N. and Dufresne, A. (2014) Nanocellulose in biomedicine: current status and future prospect. European Polymer Journal, 59, 302-325. Zhang, Z., Sèbe, G., Rentsch, D., Zimmermann, T. and Tingaut, P. (2014) Ultralightweight and flexible silylated nanocellulose sponges for the selective removal of oil from water. Chemistry of Materials, 26, 2659-2668. Every year several hundred million tons of paper are produced. Production in 2013 amounted to 402.6 million tons, which is 57 kg of paper per person (The Statistic Portal 2016). The industry has rapidly switched to production of packaging materials made of paper: 47.5% – packaging material, 40.5% – office paper, 7.7% – hygiene paper, and 4.3% – special paper, such as money or securities (Confederation of European Paper Industry 2016). Environmentally friendly packaging materials can save the World; especially, usage of reusable, recyclable and biodegradable packaging materials. Nowadays, the packaging manufacturing companies are offering environmentally friendly materials with a high proportion of recycled paper. This research is focused on making eco-friendly packaging materials using 100% recycled paper – recycled newspapers, magazines, carton boxes and office papers (V.L.T. Ltd, Latvia). In this work, the influence of natural additive – chitosan (medium molecular weight with a deacetylation degree of 70%) – on physical–mechanical properties, air permeability, antimicrobial properties and biodegradability of recycled paper packaging materials was investigated. The mechanical properties were evaluated using FRANK Tensile Tester (DIN EN ISO 1924-1 standard), but the air permeability was detected using L&W Air Permeance Tester. Recycled paper packaging materials were assessed against Staphylococcus aureus (S. Aureus ATCC 25923, gram-positive) and Escherichia coli (E. Coli ATCC 25922, gram-negative) as model bacteria by inhibition zone formation, and composted up to 40 days. The results showed that the obtained prototype of an egg box has better mechanical and wet strength properties than the analogues available on the market (Table 1). The additive of the chitosan solution does not affect significantly the air permeability of the sample. Table 1: Physical-mechanical properties and air permeability of the prototype and the analogues available on the market. Tensile index, Nm g–1 Air permeability, ml Grammage, Sample –2 min–1 gm Dry Wet 428 ± 7 3.5 ± 0.2 2.52 ± 0.13 610 ± 12 A 593 ± 9 5.41 ± 0.13 0.43 ± 0.08 635 ± 21 B 455 ± 4 3.3 ± 0.3 2.3 ± 0.2 628 ± 14 C 514 ± 6 6.3 ± 0.4 3.8 ± 0.3 630 ± 17 Prototype The results of antibacterial tests confirmed that prototype of an egg box inhibited the growth and development of S. aureus and E. coli; the stronger antimicrobial properties to E. coli culture comparing to S. aureus culture. Other eggs boxes, analogues available 46 47 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II on the market (A, B and C) showed no antimicrobial efficiency. The gravimetric test results showed (Table 2) that after 5 days in compost the samples of egg boxes have composed by 10%, after 10 and 15 days – by 20–30%, after 20 days – by 40–42%, after 25 days – more than 50%, after 30 days – by 65–70%, and after 35 days – by 80–85%. Cellulose-based controlled-release agrochemicals formulation. Table 2: The gravimetric evaluation of biodegradability of the prototype and the analogues available on the market. Weight loss, % Sample 5 days 10 days 15 days 20 days 25 days 30 days 35 days 9 20 32 42.5 55 69 84 A 11.5 21.5 34 43 50 65.5 79.5 B 8.5 19 30 40.5 50 71 85 Prototype Alena Šišková1, Piotr Rychter2, Andrej Opálek3, William Porzio4, Angela Kleinová1, Ivica Janigová1, Anita Eckstein Andicsová1 1 Polymer Institute SAS, Dúbravská cesta 9, 84541 Bratislava, Slovakia; [email protected], anita.andicsova@savba,sk Jan Długosz University, Institute of Chemistry, Environment Protection and Biotechnology 42-200 Czestochowa, Armii Krajowej 13/15. Poland; 2 Institute of Materials and Machine Mechanics SAS, Dúbravská cesta 9, 84513 Bratislava, Slovakia; 3 In addition, after 40 days the degree of the degradability was near to 95–100%; it was not possible to separate precisely from compost all the undecomposed small parts of the sample, therefore the degradability was observed visually. No significant differences between the prototype and the analogues currently available on the market have been discovered. A prototype of a moulded fibre paper material with the chitosan additive has been developed and its properties in comparison with the analogues existing on the market – determined. The mechanical strength of the prototype exceeds by approximately 20% comparing to the analogues and the wet strength of the prototype – by approximately 50%; besides the prototype shows antimicrobial properties, and it decomposes in 40 days. Acknowledgments: This research has been supported by the European Regional Devel e Fu d w h he r je “I ve ga f e fr e dly lded a er f bre a er al f r u e f f d a k g w h add ve fr re ewable re ur e ”, No. 2DP/2.1.1.1.0/14/APIA/VIAA/042. REFERENCES Confederation of European Paper Industry, http://www.cepi.org/node/19364 (seen 19.02.2016.). Production of paper and board in Europe in full transformation. The Statistic Portal, http://www.statista.com/statistics/270314/production-of-paper-andcardboard-in-selected-countries/ (seen 19.01.2016.). Production volume of paper and cardboard worldwide 2006 to 2013. 48 4 Institute of Macromolecular Chemistry CNR, E. Bassini 15, 20133 Milano, Italy. Keywords: cellulose, chemical modifications, click reaction, controlled release systems, pesticides. ABSTRACT Because of the increasing contamination of groundwater and soil caused by human agriculture activity, especially by treatment of crops by harmful substances, there are the growing demands for systems of controlled release of agrochemicals. The main objective of this research is to design, prepare and characterize the material suitable for controlled release system for potential use in agri- and horti-culture. This study involving the preparation of films/fibrous mats as suitable polymer carrier for pesticides and subsequently immobilization of that plant protection chemicals what will contribute to the decrease of pesticides mobility and its leaching into the groundwater and the soil (Dubey et al. 2011). Natural polymer/pesticide form allows prolonged release of the active agent and simultaneous degradation of the polymer carrier. From natural polymers the cellulose is the most abundant material in the world and in the intended process the secondary raw cellulosic material from the waste can be used. As a model pesticide was selected metribuzin. It is herbicide widely used in agriculture. It acts by inhibiting photosynthesis by disrupting photosystem II. It has been found that it contaminated groundwater (Roberts and Hutson 1998). Several approaches to the modification of cellulose were studied. The surface modification of cellulose films/fibrous mats and simultaneously the chemical modification of cellulose in solution were carried out by specific “click” reaction (Figure 1). The modified materials were characterized by various methods such as SEM, FTIR, XRD, EAI and by thermal analysis. We were looking for clear-cut evidence of the occurrence of chemical reactions on hydroxyl functions of cellulose. This work was supported by the Slovak Grant Agency VEGA project No. 2/0142/14, by Slovak Research and Development Agency, project No. APVV 15-0528 as well as by COST FP 1205. 49 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II Influence of the particle concentration and Marangoni flow on the formation of cellulose nanocrystal films Alican Gençer, Christina Schütz, Wim Thielemans Renewable Materials and Nanotechnology Group, Department of Chemical Engineering, KU Leuven, Campus Kulak Kortrijk, Etienne Sabbelaan 53, 8500 Kortrijk, Belgium [email protected] Cellulose substrate Figure 1: Process of specific “click” reaction Cu (I) – catalyzed azide – alkyne cycloaddition. Keywords: colloidal stability, Marangoni flow, optical properties ABSTRACT REFERENCES Dubey. S., Jhelum, V. and Patanjal P.K. (2011). Controlled release agrochemical formulations: A review. Journal of Scientific & Industrial Research, 70, 105-112. Roberts, T.R., Hutson, D.H. (1998). Metabolic Pathways of Agrochemicals: Herbicides and plant growth regulators. Royal Society of Chemistry, Thomas Graham House, Cambridge, 1998. Cellulose nanocrystals, rod-like crystalline nanoparticles are a bio-based material that can be a great alternative to obtain films with tunable optical properties. Iridescent and light diffracting films can readily be obtained via the drying of a suspension of cellulose nanocrystals.(Lagerwall et al., 2014) This deposition of the particles together with the self-assembly in the suspension has a direct effect on the optical properties of obtained films. The particle deposition onto a substrate is affected by the flow dynamics inside sessile droplets which usually yields a ring-shaped deposition pattern.(Deegan et al., 1997) We thus set out to investigate the deposition process and to control it in order to be able to generate the desired deposition pattern. To do this, we controlled the deposition patterns of the cellulose nanocrystal films by drying the films in different environments. We could thus obtain iridescent films with a uniform thickness by exerting control over the relative magnitude of the Marangoni flow and the colloidal stability of cellulose nanocrystal dispersions. Figure 1 Photographs of cellulose nanocrystal films and uniform deposition by the means of Marangoni flow REFERENCES Lagerwall, J. P. F., Schutz, C., Salajkova, M., Noh, J., Hyun Park, J., Scalia, G., & Bergstrom, L. (2014). Cellulose nanocrystal-based materials: from liquid crystal selfassembly and glass formation to multifunctional thin films. NPG Asia Mater, 6, e80. Deegan, R. D., Bakajin, O., Dupont, T. F., Huber, G., Nagel, S. R., & Witten, T. A. (1997). Capillary flow as the cause of ring stains from dried liquid drops. Nature, 389(6653), 827-829. 50 51 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II Bio-based foams from renewable and sustainable polyols obtained by liquefaction of lignocellulosics kept under 33% to avoid the recondensation reactions The strong hydrogen bonding contained in lignocellulosics is a result of the large number of hydroxyl groups present in the molecular chains of biopolymers. During liquefaction process, the polyhydric alcohols and acid catalysts lead the disrupting hydrogen bonding with additional hydroxyl groups to struggle with the cellulose inter- and intra-chain hydrogen hydrogen bonding and their large size impels the chains apart. This phenomena reduce the efficiency of the process causing recondensation reaction (Yaoguang et al. 1996). Tufan Salan1, M. Hakkı Alma2 1 Kahramanmaras Sutcu Imam University, Department of Materials Science and Engineering, Avsar Campus, 46100, Kahramanmaras, Turkey. [email protected] 2 Kahramanmaras Sutcu Imam University, Department of Forest Industry Engineering, Avsar Campus, 46100, Kahramanmaras, Turkey. [email protected] Keywords: Bio-polyols, foam, lignocellulosic biomass, liquefaction ABSTRACT Foams are one of the most useful three dimensional materials with great versatility because they can be used in various forms in several applications areas such as packaging, cushioning and insulation. Polymeric foams involve polyurethane foam (PUF), polystyrene foam (PSF) and phenolic foam (PF). The production of these materials consist of varied processing conditions such as gaseous extrusion of molten polystyrene (PS) into foam while the reaction of selected polyols (polyether and polyester) and isocyanate with a blowing agent generate PUF. On the other hand, the PF manufacturing procedure needs the usage of a heat/acid reactive resole type phenolic resin, emulsifier, a volatile blowing agent and an acid catalyst (Pilato 2010). The major drawback of these petroleum-based foams is that they are typically manufactured from non-renewable, non-recyclable and not-biodegradable raw materials. Accordingly, due to increasing concerns about fossil sources lignocellulosics has become an attractive alternative for the production of bio-based materials. Lignocellulosics such as agricultural and forestry wastes naturally involve bio-polymers such as cellulose, hemicellulose, lignin and tannin which contain more than one hydroxyl group in the molecular chains. The liquefaction method is an effective way to convert lignocellulosic feedstock into intermediate bio-polyols which can be used as a starting raw material for the production of green polymers. Liquefaction of lignocellulosic biomass in the presence of organic solvents became a popular research area over the last decade. The polyhydric alcohols and phenol are the most used solvents while different organic solvents have been used in liquefaction reaction. So far, the liquid products obtained after liquefaction of biomass have been applied to preparation of novolak and resol type phenolic resins, Bakelite like molding materials, carbon fibers, polyesters, epoxy resins, resol type PF and PUF. It has been proven by many scientists that the liquefied biomass obtained using polyhydric alcohols such as polyethylene glycol (PEG), glycerol or their mixtures as liquefaction solvents could be used directly as polyols for the manufacturing of PUFs without additional treatment. These foams were produced in three different structures comprised the rigid type using polymeric methylene diphenylene diisocyanate (PMDI) (Alma and Basurk 2003), semi-rigid type using polyaryl polymethylene isocyanate (PAPI) (Gao et al. 2010), and flexible type using toluene diisocyanate (TDI) (Zhang et al. 2012). Polyurethane foams are typically produced from polyols with hydroxyl numbers ranging from 300-500 mg KOH/g while biomass typically has hydroxyl numbers around 1500 mg KOH/g. Therefore, the amount of biomass used have to be 52 PFs have attracted great attention due to its perfect fire resistant, low fire toxicity, high dimensional stability, and low thermal conductivity comparing the other foam types. There are a few studies regarding the preparation PF from liquefied lignocellulose based resol resin. Lee et al (2002) liquefied the wood into phenol in the presence of sulfuric acid catalyst at a moderate temperature of 150 °C under constant stirring and reflux. The liquefied wood was used to prepare resol resin by the reaction with formaldehyde under alkaline conditions. The obtained liquefied wood-based resol resin was applied for the preparation of the phenolic foam. The resin mixed together with the poly (ethylene ether) of sorbitan monopalmitate as a surfactant, hydrochloric acid as a catalyst, and diisopropyl ether as a blowing agent. The obtained foams showed satisfactory densities and compressive properties, comparable to those of foams obtained from conventional resol resin. The resol-type resin was also prepared from the liquefied products of walnut shell into phenol by Huang et al (2011). They successfully applied the biomass-based resol resin to produce phenolic foam with diisopropyl ether as the blowing agent, Tween 80 as the surfactant and hydrochloric acid as the catalyst, respectively. The obtained foams showed satisfactory mechanical properties and a uniform fine cellular structure. REFERENCES Alma, M.H., Basturk M.A. (2003). New polyurethane-type rigid foams from liquified wood powders. Journal of Materials Science Letters, 22, 1225 – 1228. Gao, L. L., Liu, Y. H., Lei, H., Peng, H., Ruan, R. (2010). Preparation of semirigid polyurethane foam with liquefied bamboo residues. Journal of Applied Polymer Science, 116(3), 1694-1699. Huang, Y., Zheng, Z., Feng, H. Pan, H. (2011). Phenolic foam from liquefied products of walnut shell in phenol, Advanced Materials Research 236-238, 241-246. Lee, S.-H., Teramoto, Y., Shiraishi, N. (2002). Resol-type phenolic resin from liquefied phenolated wood and its application to phenolic foam. Journal of Applied Polymer Science, 84, 468–472. Pan, H., Zheng, Z., Hse, C.Y. (2012). Microwave-assisted liquefaction of wood with polyhydric alcohols and its application in preparation of polyurethane (PU) foams. European Journal of Wood and Wood Products, 70(4), 461-470. Pilato, L. (2010). Phenolic Resins: A Century of Progress, Springer-Verlag Berlin Heidelberg, USA, 534 p. Yaoguang, Y., Yoshioka, M., Shiraishi, N. (1996). Water absorbing polyurethane foams from liquefied starch, Journal of Applied Polymer Science, 60, 1939-1949. Zhang, J.P., Du, M. H., Hu, L.S. (2012). Bamboo liquefaction with polyhydric alcohols and its application in flexible polyurethane foam. Advanced Materials Research 524, 2113-2117. 53 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II Analytical methods for the investigation of the water - biodegradable films interaction Interaction of water with CNC films Bianca-Ioana Dogaru, Maria-Cristina Popescu, Carmen-Mihaela Popescu Petru Poni Institute of Macromolcular Chemistry of the Romanian Academy, Iasi, Romania [email protected], [email protected], [email protected] Imola Herceg, Emília Csiszár Budapest University of Technology and Economics, Department of Physical Chemistry and Materials Science, H-1521 Budapest, Hungary. [email protected], [email protected] Keywords: surface energy, water sorption, contact angle, amino-aldehyde resin ABSTRACT Keywords: water sorption, NIR spectroscopy, contact angle measurements ABSTRACT Water plays an essential role in all living bodies and the hydrogen bonding between water molecules is induced by the electrostatic interaction between the negative oxygen atom and positive hydrogen atom of a neighboring water molecule. In aqueous polymer systems, interaction between water and a polymer chain is highly important to determine the physical properties of the systems in wide concentration regions. On the other side, water sorbed into polymeric materials, in solid state, from the air or the aqueous medium often causes a significant change in mechanical properties of the polymers and suggests the domain of applicability. In this context, the understanding of the effect of absorbed water molecules (moisture) on the molecular interactions and relaxation dynamics in polymer networks is an interesting and fundamentally important problem. The sorption of water molecules induces usually swelling behavior is a polymeric network. The later one depends on the polymer nature, composition of polymeric system, molecular mass, degree of crosslinking and the compatibility between the polymer and the solvent. Two types of water, hydrated water and bulk water, are distinguishable in the vicinity of a polymer/water interface. Hydrated water is sorbed inside of the polymer matrix where molecular interactions are involved; whereas bulk water exists outside of the polymer matrix as liquid water. In the present study, the interaction between water molecules and PVA/S/CNC film has been explored by water vapor sorption tests, NIR spectroscopy and contact angle measurements. The water vapor sorption was evaluated by static method using the saturated salts solutions with different values of the RH. It has been observed that the amount of water adsorbed decrease with the increasing of the S and CNC content. At the same time, information on the amount and interactions involved were obtained from the bands assigned to O-H stretching from water molecules from the NIR spectra. Over the past twenty years, there has been intense and continuing interest in the development of new and high value-added cellulose based materials to increase the use of cellulose in consumer and industrial products. Currently, the fastest growing research activity is concentrating on nanocelluloses, the novel forms of cellulose, because they are renewable, environmentally sound and biodegradable. Of the three main types of nanocelluloses (i.e. microfibrillated, nanocrystalline and bacterial nanocellulose), the cellulose nanocrystals (CNC) are prepared from different cellulose containing sources, such as lignocellulose based biomass, wood, cellulosic fibres, etc. by removal of the amorphous phase with acid hydrolysis usually followed by an ultrasonic treatment in order to disintegrate the aggregates of liberated crystalline cellulose particles. Nanocelluloses can be used in several areas. Recent results proved that nanocellulose based films can be good candidates for packaging materials in different fields (Oksman et al., 2016; Kontturi et al. 2006) In this research cellulose nanocrystals (CNC) were prepared from bleached cotton fibres with sulphuric acid hydrolysis (Csiszar et al. 2016), and from the CNC suspension nanocomposite films were prepared wherein the cellulose nanowhiskers were crosslinked with an amino-aldehyde resin. The water-film interaction and the surface energy of the films were systematically evaluated by measuring the contact angle and the water sorption capacity as a function of the resin content (from 0 % to 30 %). Results revealed that the increasing concentration of resin was associated with lower moisture uptake by the films. At higher resin concentration the disintegration rate of films by water decreased significantly. REFERENCES Oksman, K., Aitomäki, Y., Mathew, A.P., Siqueira, G., Zhou, Q., Butylina, S., Tanpichai, S., Zhou, X., Hooshmand, S. (2016) Review of the recent developments in cellulose nanocomposite processing, Composites: Part A, 83, 2-18. Kontturi, E., Tammelin, T., Österberg, M. (2006) Cellulose – model films and the fundamental approach. Chem. Soc. Rev., 35, 1287-1304. Csiszar, E., Kalic, P., Kobol, A. and Ferreira, E.P. (2016). The effect of low frequency ultrasound on the production and properties of nanocrystalline cellulose suspensions and films. Ultrasonics & Sonochemistry, 31, 473-480. 54 55 COST ACTION FP1205 BUDAPEST 22-23 September 2016 COST ACTION FP1205 BUDAPEST 22-23 September 2016 Poster presentations II COST ACTIONPoster FP1205 presentations BUDAPEST 22-23 September 2016 II Nanocomposite films based on cellulose nanocrystals and titanium dioxide nanoparticles Bio-inspired nanocomposite films and foams from resilin-CBD bound to cellulose nanocrystals David Leibler, Oded Shoseyov T. Ben Shalom1, A. Rivkin1, T. Abitbol1, Yuval Nevo1, 2, S. Lapidot2 and O. Shoseyov1 The Hebrew University of Jerusalem, The Robert H. Smith Faculty of Agriculture, Food and Environment, P.O.B 12 Rehovot, Israel. [email protected] Keywords: cellulose nanocrystals, TiO2 nanoparticles, UV-blocking 1 The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew University of Jerusalem, Rehovot 76100, Israel. [email protected] 2 Melodea Ltd. The Robert H. Smith Faculty of Agriculture, Food and Environment, the Hebrew Universit y of Jerusalem, Rehovot 76100, Israel ABSTRACT Preliminary studies were conducted to assess the properties and stability of aqueous mixtures of cellulose nanocrystals (CNCs) and TiO2 nanoparticles (NPs) using dynamic light scattering (DLS) and zeta-potential measurements. Conditions (e.g., pH, concentration) were found where the mixtures were colloidally stable, essentially at pH values where both types of NPs had a negative surface charge. The stable NP mixtures were cast into films that possessed mechanical properties similar to neat CNC films but optical properties (i.e., UV-blocking) related to the TiO2 NPs. These films are of interest for UV-blocking cellulosic coatings that may be useful for various applications, such as in packaging. Keywords: Bio composite, cellulose nanocrystals, resilin, self-assembly ABSTRACT The arthropod cuticle and the plant cell wall are examples of the remarkable composite materials that support survival in nature. Inspired by the elasticity of insect's cuticle and the strength of plants cell wall, E. coli was genetically engineered in order to produce recombinant resilin fused to a cellulose binding domain (res-CBD). The rubbery characteristics of resilin-like proteins and the binding of the res-CBD to cellulose nanocrystals (CNCs) has been previously explored by our group (Qin el al. 2011, Rivkin et al. 2015). The isolation and purification of cellulose nanocrystals involves a simpler, bottomdown approach, where CNCs are most commonly extracted by sulfuric acid hydrolysis of native cellulose. CNCs from sulfuric acid hydrolysis form stable suspensions in water due to repulsive interactions from charged groups grafted on during hydrolysis and exhibit interesting self-assembly, optical and mechanical properties that make them suited for a wide range of applications. In terms of mechanical properties, resilin and CNCs are very different. The structure of resilin, essentially an amorphous, hydrogel polymer, held together via di- and trityrosine crosslinks, imparts near perfect elasticity. In contrast to the flexibility and relative softness of the resin, CNCs are highly crystalline, hydrogen bonded and structured that imparts strength and stiffness that comparable to steel and Kevlar®. This work explores the properties of bionanocomposite foams and films prepared by binding res-CBD to CNCs. REFERENCES Qin G, Rivkin A, Lapidot S, Hu X, Preis I, Arinus SB, Dgany O, Shoseyov O and Kaplan DL (2011). Recombinant exon-encoded resilins for elastomeric biomaterials. Biomaterials. 32, 9231-43. Rivkin A, Abitbol T, Nevo Y, Verker R, Lapidot S, Komarov A, Veldhuis S.C, Zilberman G, Reches M, Cranston E.D and Shoseyov O. (2015). Bionanocomposite films from Resilin-CBD bound to Cellulose Nanocrystals. Industrial Biotechnology. 11, 44-58. 56 57 COST ACTION FP1205 BUDAPEST 22-23 September 2016 ABOUT COST COST (European Cooperation in Science and Technology) is a pan-European intergovernmental framework. Its mission is to enable break-through scientific and technological developments leading to new concepts and products and thereby contribute to strengthening Europe’s research and innovation capacities. It allows researchers, engineers and scholars to jointly develop their own ideas and take new initiatives across all fields of science and technology, while promoting multi- and interdisciplinary approaches. COST aims at fostering a better integration of less research intensive countries to the knowledge hubs of the European Research Area. The COST Association, an International notfor-profit Association under Belgian Law, integrates all management, governing and administrative functions necessary for the operation of the framework. The COST Association has currently 36 Member Countries. www.cost.eu 58