Fibrillated Cellulose and Block Copolymers as a Modifiers of Unsaturated Polyester Nanocomposites Daniel H. Builes, Hugo Hernández, Laida Cano, Agnieszka Tercjak Group Materials + Technologies Polymeric and Renewable Materials Technological Development Center Madrid, May 20 2014
Aim of this Work To establish a pathway for mechanical isolation of cellulose nanofibrils from sisal fibers and to employ them as reinforcement of unsaturated polyester thermosets in order to produce a nanocomposite material with improved mechanical properties and high transparency Group Materials + Technologies 2
PARTS OF THE PRESENTATION 1. INTRODUCTION 2. Modification of an unsaturated polyester matrix with the PEO-b-PPO-b-PEO block copolymer E 20 P 69 E 20 (EPE20) 3. Preparation of sisal microfibrillated cellulose (MFC) 4. Nanocomposites based on unsaturated polyester and microfibrillated cellulose (MFC) 5. CONCLUSIONS Group Materials + Technologies 3
INTRODUCTION H O phthalate O O O O propylene O O O fumarate diethylene O OH n Oligomer of Unsaturated Polyester (UPol) Unsaturated Polyester Resin (UP) An UP resin is a mixture of UPol with styrene Cristalán 860: Orthophtalic UP resin with 36 wt % of St Manufactured by Andercol S.A. 4
Curing Process INTRODUCTION Curing process of UP resin is a free-radical chain polymerization, exothermic and inhomogeneous process UP resin Growth of chains Cyclization of chains Phase separation (microgels formation) Microgel-Microgel Crosslinking (Percolation) 5
Block Copolymers (BCP) INTRODUCTION A BCP is produced linking by covalent bonds two or more homopolymers thermodynamically incompatible to create a novel macromolecule with hybrid properties PS-b-PI-b-PEO triblock copolymer Polystyrene Polyethylene oxide Polyisoprene m 6
INTRODUCTION PEO - b - PPO - b - PEO O O CH 3 O OH Structure Scheme Name E 20 P 69 E 20 EPE20 E 5 P 68 E 5 EPE5 PEO miscibility with UP resins is higher than the PPO miscibility Group Materials + Technologies 7
PARTS OF THE PRESENTATION 1. INTRODUCTION 2. Modification of an unsaturated polyester matrix with the PEO-b-PPO-b-PEO block copolymer E 20 P 69 E 20 (EPE20) 3. Preparation of sisal microfibrillated cellulose (MFC) 4. Nanocomposites based on unsaturated polyester and microfibrillated cellulose (MFC) 5. CONCLUSIONS Group Materials + Technologies 8
Mixtures Before Curing (non-reactive mixtures) Temperature ( C) UP UP + 5 wt % EPE5 UP + 50 wt % EPE20 120 100 80 60 (two phases) (one phase) 0 10 20 30 40 50 60 70 EPE20 content in UP (wt %) Visual appearance of non-reactive mixtures compared with neat UP resin at room temperature LCST behaviour of UP/EPE20 mixtures Builes, D. H. et al Polymer 53, 3669 (2012) 9
Dynamic Light Scattering (DLS) Colloidal particles in a liquid (Brownian motion) Scattering Angle ( ) Smaller particles Autocorrelation function 10
Dynamic Light Scattering (DLS) Sample without particles Colloidal particles in a liquid (Brownian motion) Scattering Angle ( ) No autocorrelation function 11
Dynamics of Nonreactive Mixtures (DLS) Mixtures of UP + EPE20 Autocorrelation fuction vs EPE20 content Autocorrelation fuction vs Temperaure 12
Differential Scanning Calorimetry (DSC) Nonreactive mixtures of UP + EPE20 13
Cured Mixtures Group Materials + Technologies
tan d tan d Dynamical Mechanical Analysis (DMA) Cured at 80 C 0,5 Cured at 25 C 0,3 Neat UP UP+15%EPE20 0,4 Neat UP UP+15%EPE20 0,2 0,3 0,2 0,1 0,1 0,0 25 75 125 175 225 Temperature ( C) 0,0 25 75 125 175 Temperature ( C) Group Materials + Technologies 15
Normalised Heat Flow endo tan d DSC 0,3 0,2 0,1 15%EPE20 UP 0,0 25 75 125 175 225 Temperature ( C) EPE20 UP + 15%EPE20 (80 C) UP + 15%EPE20 (25 C) Neat UP -90-60 -30 0 30 60 Temperature ( C) Group Materials + Technologies 16
tan d Neat UP Morphology (AFM) Neat UP 0,3 Neat UP 0,2 0,1 0,0 25 75 125 175 225 Temperature ( C) 100 nm 20 nm Group Materials + Technologies 17
UP + 5 wt % EPE20 Mixtures Morphology (AFM) (cured at T 60 C) UP + 15 wt % EPE20 100 nm 100 nm 100 nm 100 nm Builes, D. H. et al ACS Appl Mater Interfaces 6, 1073 (2014) 18
UP + 5 wt % EPE20 Mixtures Morphology (AFM) (cured at 25 C) UP + 15 wt % EPE20 100 nm 100 nm 100 nm 100 nm Builes, D. H. et al J Phys Chem C 117, 3563 (2013) Group Materials + Technologies 19
PARTS OF THE PRESENTATION 1. INTRODUCTION 2. Modification of an unsaturated polyester matrix with the PEOb-PPO-b-PEO block copolymer E 20 P 69 E 20 (EPE20) 3. Preparation of sisal microfibrillated cellulose (MFC) 4. Nanocomposites based on unsaturated polyester and microfibrillated cellulose (MFC) 5. CONCLUSIONS 21
Cellulose Fibers as Reinforcement Sustainability Hierarchical structure Low density Recyclability Biodegradability Good mechanical properties: (elastic modulus from 130 to 250 GPa in the crystalline regions) Renewability Group Materials + Technologies 22
Hierarchical Structure Fibre Macrofibrils Cellulose chains Microfibrils Group Materials + Technologies 23
Homogenization Technique Microsizing zone Microsized fibres Premix Impact head Valve shaft Passage head Aqueous suspensions sisal cellulose fibers during homogenization process after several passes Number of passes: 10 40 60 100 120 24
Size Monitoring (Optical Micrographs) Cellulose fibers during mechanical homogenization process 500 mm 500 mm 10 passes 40 passes 500 mm 60 passes 500 mm Builes, D. H. t al Compos Sci Technol 89, 120 (2013) 100 passes 5 mm 25
Microfibrillated Sisal Fibers (AFM) 160 nm 50 nm 10 nm 5 mm x 5 mm 1 mm x 1 mm Group Materials + Technologies 26
PARTS OF THE PRESENTATION 1. INTRODUCTION 2. Modification of an unsaturated polyester matrix with the PEO-b-PPO-b-PEO block copolymer E 20 P 69 E 20 (EPE20) 3. Preparation of sisal microfibrillated cellulose (MFC) 4. Nanocomposites based on unsaturated polyester and microfibrillated cellulose (MFC) 5. CONCLUSIONS
Intensity (%) Hydrodynamic Diameter (DLS) 100 - - - - MFC in water -. -. - Aqueous solution of EPE20 MFC in water solution of EPE20 MFC in water Aqueous solution of EPE20 MFC in aqueous solution of EPE20 50 0 10 0 10 1 10 2 10 3 10 4 Hydrodynamic diameter (nm) Group Materials + Technologies 28 28
Two different thermosetting systems based on UP resin were prepared: 1. UP + 1 wt % MFC 2. UP + (1 wt % MFC + 5 wt % EPE20) Group Materials + Technologies 29
Neat UP UP+MFC UP + 1 wt % MFC UP +1 wt % MFC + 5 wt % EPE20 200 mm 200 mm 200 mm Optical Micrographs of Cured Samples Group Materials + Technologies 30
Transmittance (%) Transparency Ultraviolet-visible Spectroscopy (UV-vis) 80 60 40 20 0 Neat UP 5%EPE20 UP + 5 % EPE20 1%MFC UP + 1 % MFC 1%MFC5%EPE20 UP + 1 % MFC+5 % EPE20-20 200 400 600 800 Wavelength (nm) Group Materials + Technologies 31 31
Morphology (AFM ) MFC 100 nm Neat UP UP + 5 wt % EPE20 UP + 1 wt % MFC + 5 wt % EPE20 Group Materials + Technologies 32
Mechanical Properties Load Load 200 mm 33
Fracture Surface 50 mm Neat UP UP+ 5 wt % EPE20 UP + 1 wt % MFC + 5 wt % EPE20 34
APPLICATIONS Transparency is not required Transparency is required Group Materials + Technologies 35
CONCLUSIONS A block copolymer with structure E 20 P 69 E 20 (EPE20) was used as an effective nanostructuring agent to increase the toughness of a commercial UP resin Self-assembly mechanism was responsible for the nanostructuration of the UP resin modified with EPE20 block copolymer A new pathway to fabricate nanocomposites of UP/MFC/EPE20 was developed by means of a controlled nanostructure achieving an appropriate reinforcement/transparency balance Group Materials + Technologies 36
ACKNOWLEDGMENTS To Andercol S.A. To Group Materials + Technologies (GMT) University of the Basque Country (UPV/EHU) Group Materials + Technologies
Publications Builes, D. H.; Tercjak, A.; Mondragon, I. Polymer 53, 3669 (2012) Nanostructured Unsaturated Polyester Modified (ethylene oxide)] Triblock Copolymer Builes, D. H.; Hernández, H.; Mondragon, I.; Tercjak, A. J Phys Chem C 117, 3563 (2013) with Poly[(ethylene oxide)-b-(propylene oxide)-b- Relationship between the Morphology of Nanostructured Unsaturated Polyesters Modified with PEO-b-PPO-b-PEO Triblock Copolymer and their Optical and Mechanical Properties Builes, D. H.; Labidi, J.; Eceiza, A.; Mondragon, I.; Tercjak, A. Compos Sci Technol 89, 120 (2013) Unsaturated Polyester Nanocomposites Modified with Fibrillated Cellulose and PEO-b-PPO-b-PEO Block Copolymer Builes, D.; Hernández-Ortiz, J. P.; Corcuera, M. A.; Mondragon, I.; Tercjak, A. ACS Appl Mater Interfaces 6, 1073 (2014) Effect of Poly(ethylene oxide) Homopolymer and Two Different Poly(ethylene oxide-b-poly(propylene oxide)-b-poly(ethylene oxide) Triblock Copolymers on Morphological, Optical, and Mechanical Properties of Nanostructured Unsaturated Polyester
Thank you! daniel.builes@andercol.com.co Group Materials + Technologies