Using RAFT Chemistry to produce ‘Next Generation’ Carbon Fibre Webinar 1 Dec 2015 Using RAFT Chemistry to produce ‘Next Generation’ Carbon Fibre Jackie Cai Keith Millington Shaun Smith CSIRO Manufacturing 1 December 2015 Advanced Fibre Innovation Group CSIRO Manufacturing Waurn Ponds VIC 3216 Presentation Overview 1. 2. 3. 4. 5. 6. CSIRO- who we are RAFT polymerisation Carbon fibre R&D - background Making PAN precursor using RAFT What happens next? Questions and discussion 3 | RAFT PAN precursor Webinar December 1st 2015 CSIRO People 6000 Sites 55 Business Units Budget Darwin Cairns Atherton Townsville 9 2 sites Alice Springs $1B+ Rockhampton Bribie Island 64% of our people hold Murchison We develop 832 postgraduate research students with our university partners 4 | RAFT PAN precursor Webinar December 1st 2015 Brisbane 6 sites Gatton university degrees over 2000 hold doctorates over 500 hold masters Toowoomba Myall Vale Narrabri Geraldton 2 sites Armidale 2 sites Mopra Perth 3 sites Newcastle Parkes Adelaide 3 sites Irymple Griffith Wodonga Werribee 2 sites Geelong Sydney 5 sites Canberra 7 sites Melbourne 5 sites Hobart Sandy Bay Our Business Units AGRICULTURE BIOSECURITY DIGITAL PRODUCTIVITY AND SERVICES FOOD AND NUTRITION LAND AND WATER MANUFACTURING MINERAL RESOURCES OCEANS AND ATMOSPHERE 5 | RAFT PAN precursor Webinar December 1st 2015 ENERGY Manufacturing People 400 Sites Budget 5 $110m Each year we work with over 1100 firms Sydney Canberra Geelong Melbourne (Clayton & Parkville) 6 | RAFT PAN precursor Webinar December 1st 2015 Manufacturing Research Programs 1. 2. 3. 4. High Performance Metal Industries Industrial Innovation Biomedical Manufacturing Advanced Fibre and Chemical Industries 7 | RAFT PAN precursor Webinar December 1st 2015 2. RAFT Polymerisation What is RAFT Technology? Traditional Free Radical Polymers MONOMER R A F T In In Initiator In In MW •Reversible •Addition •Fragmentation RAFT Controlled Polymers •chain Transfer S R MONOMER S Z Initiator MW 9 | RAFT PAN precursor Webinar December 1st 2015 More than just control of PDI • Can design and build complex molecules • Range of functionalities and architectures • New and improved performance 10 | RAFT PAN precursor Webinar December 1st 2015 RAFT – It’s not just CSIRO • CSIRO IP portfolio comprised of 10 patent families 7000 cumulative publications • Foundation patents (around process) • Patent coverage to 2018 to 2030 • >100 companies have filed >400 patents on RAFT based products and processes. 6000 total publications on RAFT 5000 4000 3000 papers 2000 1000 patents 0 2000 2005 year • RAFT Agents are available commercially • Sigma Aldrich, Monomer Polymer, Strem and Boron Molecular 11 | RAFT PAN precursor Webinar December 1st 2015 2010 The Global Impact of RAFT Commercial products in market Used across many market areas Asteric™ Viscosity Modifiers 12 | RAFT PAN precursor Webinar December 1st 2015 Good news 13 | RAFT PAN precursor Webinar December 1st 2015 3. Carbon fibre R&D - background Carbon fibre manufacturing 15 | RAFT PAN precursor Webinar December 1st 2015 Grades of carbon fibre (Toray) Both T grades (high strength) and M grades (high modulus) are produced from different formulations of PAN with copolymers (up to 5%). Polymer properties and spinning and conversion parameters are confidential 16 | RAFT PAN precursor Webinar December 1st 2015 Precursor composition Theoretical maximum strength of carbon fibre is ~100 GPa Strongest commercial grades (eg. T1000) have 7.5 GPa The exact composition of the precursor for each grade varies from one company to another and is generally considered a trade secret Optimising the structure and evenness of the precursor fibre should improve strength of carbon fibre 17 | RAFT PAN precursor Webinar December 1st 2015 PAN precursor R&D 18 | RAFT PAN precursor Webinar December 1st 2015 4. Making PAN precursor using RAFT Reported literature on RAFT polymerization for PAN-based precursors Scientific literature to date has reported either:• Low molecular weight (<100 kDa) and low PDI (e.g. 1.1), or • High molecular weight (100-200 kDa) and very high PDI (≥ 1.6) 20 | RAFT PAN precursor Webinar December 1st 2015 February 2014 Mn = 133 kDa PDI = 1.34 MMA copolymer January 2008 Mn = 200 kDa PDI = 1.7 MA, IA, MMA copolymer 21 | RAFT PAN precursor Webinar December 1st 2015 CSIRO Patent lodged in March 2013 Priority date March 15 2013 Mn >200 kDa PDI < 1.3 MMA, MA, IA copolymer 22 | RAFT PAN precursor Webinar December 1st 2015 Excellent control to synthesise a high molecular weight precursor has been achieved by: Using the most suitable RAFT agents Using a solvent with a low chain transfer constant A high [M] : [RAFT] ratio (> 4000) A relatively low [RAFT] : [initiator] ratio (≤ 2.5) Relatively low polymerisation temperature Specific temperature profile 23 | RAFT PAN precursor Webinar December 1st 2015 Examples of RAFT agents and comonomers S CH3 C S C S CN RAFT Agents CH3(CH2)10CH2 S CH3 C S R R’ = (3) CH3 , (4) CH2CH3 or (5) CH2CH2COOH S C COOH S CH2 CH COOH CH + H2C CH CN COOCH3 CN R' R = (1) CH3 or (2) CH2CH2COOH H2C C + H2C C CN CH2 CH COOCH3 n CH2 C CH2 m C j CN R COOH RAFT CH2 COOH S CH3(CH2)10CH2 S C S COOH CH2 CH CN CH2 CH n COOCH3 December 1st 2015 CH3 CH2 C m CH2 COOH 24 | RAFT PAN precursor Webinar CH3 C CN j R' Examples (a) Control Polymer 1 RAFT Polymer 1 Control Polymer 1 RAFT Polymer 1 Mn ≈ 340K PDI =1.95 Mn ≈ 337K PDI =1.16 22 24 (b) 26 28 30 Retension volume (mL) 32 34 Control Polymer 3 RAFT Polymer 3 25 | RAFT PAN precursor Webinar December 1st 2015 Control Polymer 3 RAFT Polymer 3 Mn ≈ 461K PDI =2.15 Mn ≈ 469K PDI =1.23 22 24 26 28 30 Retension volume (mL) 32 34 DSC Results (b) 1 Heat Flow (W/g) 0 A -1 B -2 -3 -4 C -5 heated at 5°C/min under N2 -6 150 200 250 Temperature (oC) (A) RAFT PAN terpolymer, (B) control PAN terpolymer, (C) a commercial PAN homopolymer 26 | RAFT PAN precursor Webinar December 1st 2015 300 350 183.1 – 339.8 °C 176.5 – 336.5 °C 269.6 – 303.6 °C PAN precursor fibres produced by wet spinning SEM images of the Control sample Control sample SEM images of the RAFT sample RAFT sample 27 | RAFT PAN precursor Webinar December 1st 2015 Wet spinning trials Wet spinning trials to date have used matching conditions to a control sample for comparative purposes, but these are not the optimal conditions for RAFT sample. Dope rheology is different. Higher Mn polymers have not been spun yet Therefore, further studies are being conducted to optimise the spinning conditions for RAFT precursor. 28 | RAFT PAN precursor Webinar December 1st 2015 Variation in fibre diameter is attributed to poor spinning quality Thermal conversion of white fibre at Carbon Nexus. 29 | RAFT PAN precursor Webinar December 1st 2015 White Fibre Properties – 1st Comparative Trial Precursor fiber Breaking Stress (GPa) Young's Modulus (GPa) Breaking Strain Br. Energy (J/cm3) (%) Ave CV% Ave CV% Ave CV% Ave CV% RAFT sample 1.1 3.0 12.1 14.0 15.4 7.8 83.8 7.1 Control sample 0.7 23.4 9.0 36.3 12.3 10.6 46.8 31.2 Difference % 30 | RAFT PAN precursor Webinar 49 December 1st 2015 35 25 70 Carbon Fibre Properties – 1st Comparative Trial Carbon fiber Breaking Stress (GPa) Young's Modulus (GPa) Breaking Strain (%) Ave CV% Ave CV% Ave CV% RAFT sample 3.2 25.3 268.0 18.2 1.1 23.9 Control sample 2.2 35.8 242.3 19.9 1.0 28.2 Difference % 31 | RAFT PAN precursor Webinar 45 December 1st 2015 11 10 Technical summary New RAFT polymerization process enables the production of PAN-based precursors with a Mn up to 500 kDa while still maintaining a low PDI (≤ 1.25) The initial spinning/carbonisation trial showed that RAFT precursor polymers exhibited: • Different dope rheology and spinning properties to conventional PAN (easier spinning) • Superior processing properties • Superior mechanical properties of the resultant carbon fibre Further spinning research and trials are now required 32 | RAFT PAN precursor Webinar December 1st 2015 What’s next? • Ready for industry engagement • Further wet spinning trials of RAFT PAN precursors and conversion to carbon fibre • Commercialisation of RAFT PAN technology 33 | RAFT PAN precursor Webinar December 1st 2015 Acknowledgements CSIRO Team Jill McDonnell, Lisa O’Brien, Colin Brackley, Jeff Church, Nicole Phair University of Kentucky Matt Weisenberger and his team Deakin University/Carbon Nexus Bronwyn Fox and Steve Atkiss 34 | RAFT PAN precursor Webinar December 1st 2015 What’s next? CSIRO in Australian Pavilion with Carbon Nexus 35 | RAFT PAN precursor Webinar December 1st 2015 Thank you Shaun Smith Research Group Leader t +61 3 5246 4000 e shaun.smith@csiro.au w www.csiro.au CSIRO MANUFACTURING 36 | How Austrade helps How we can help you The Australian Trade Commission, in cooperation with state and territory governments, provides free and confidential assistance: • National coordination of Australian government investment The report included case studies but they services • Information on the Australian business and regulatory environment • Market intelligence and investment opportunities • Identification of suitable investment locations and partners in Australia • Advice on Australian government programs and approval processes Australia - open for business Upcoming opportunities to engage with Australia • JEC Paris March 2016 • Innovation Forum: See Australia at its best April 2015 • Australia-Germany Advanced Materials Institute (recommendation of the Australia-Germany Advisory Group) Further details will be available shortly. Australia - open for business Thank you! Johanna Harvey, Investment Manager & WE Team Leader AMST johanna.harvey@austrade.gov.au Tel: +49 69 90558118 Mob: +49 179 6912011
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