Studies on PAN/CNC and PAN/Lignin Nanocomposites. Georgia Institute of Technology Satish Kumar s Group Presented by Jeffrey Luo

Transcription

1 Studies on PAN/CNC and PAN/Lignin Nanocomposites Georgia Institute of Technology Satish Kumar s Group Presented by Jeffrey Luo 1

2 Outline Background Polyacrylonitrile (PAN)/Carbon Nanotube (CNT) Fibers PAN/Lignin Fibers Cellulose Nanocrystal (CNC) dispersion PAN/CNC Films and Fibers Conclusions 2

3 Carbon Fiber Background Thomas Edison 1880s = Carbon Fiber (T1000G) = Carbon Fiber Composite Unidirectional (T1000G) PAN 1960s charts 2009.pdf of carbon fiber/ 3

4 Motivation Low Cost Carbon Fiber More Bio renewable Carbon Fiber Carbon Fiber with Higher Mechanical Properties Total: $9.88 Total: $ carbon_fiber_cost_breakdown 4

5 Gel Spinning Spinning Process PAN PAN/CNT PAN/Lignin PAN/CNC Methanol ( 50 C) 5

6 Stabilization and Carbonization Batch Process Lower mechanical properties than continuous process. H.Chae, Dissertation,

7 Stabilization and Carbonization Continuous Process 7

8 PAN & PAN/CNT Fiber Produced at Georgia Tech PAN PAN/CNT 8

9 PAN/CNT Carbon Fibers Templating PAN Templating around the CNTs during Carbonization GT PAN/CNT Carbon Fiber PAN Templating B. Newcomb et al., Carbon,

10 PAN/CNT Carbon Fiber Thermal Conductivity Gel spun carbon fiber has higher thermal conductivity 60% increase in thermal conductivity with addition of 1 wt% CNT. B. Newcomb et al., Carbon,

11 PAN/CNT Carbon Fiber Electrical Conductivity Incorporation of CNT and PAN templating increased electrical conductivity. B. Newcomb et al., Carbon,

12 PAN/Lignin Carbon Fiber Cross Sections Carbon Fiber Cross Sections Weight Ratio PAN 100 H C Li t l ACS S t i bl Ch i t d E i i (2015) PAN/Lignin 70/30 PAN/Lignin/CNT 70/30/3 12

13 PAN/Lignin Fibers Mechanical Properties Precursor Diameter (μm) Tensile Strength (MPa) Tensile Modulus (GPa) Strain at Failure (%) PAN 17.5 ± ± ± ± 0.6 PAN/Lignin 18.5 ± ± ± ±0.6 PAN/Lignin/CNT 17.1 ± ± ± ±0.5 Carbon Fiber Diameter (μm) Tensile Strength (GPa) Tensile Modulus (GPa) Strain at Failure (%) PAN 11.0 ± ± ± ±0.1 PAN/Lignin 11.0 ± ± ± ±0.1 PAN/Lignin/CNT 8.8 ± ± ± ±0.1 H C Liu et al ACS Sustainable Chemistry and Engineering (2015) 13

14 CNC Dispersion in Co solvent System CNC has better dispersion in a cosolvent system compared to a single solvent system. Bath sonicator 3g/100mL H. Chang et al., ACS applied materials & interfaces, (2016) 14

15 PAN/CNC Rheology Increasing viscosity in composite solution with time. Complex Viscosity at 5 rad/s (Pa*s) 1 Neat PAN-co-MAA CNC-5 CNC-10 CNC-20 CNC-30 CNC-40 Manuscript in progress Time (Days) 15

16 PAN/CNC Film Optical Transparency No decrease in optical transparency even up to 40 wt% CNC loading. 0 wt% CNC 5 wt% CNC 10 wt% CNC wt% CNC 30 wt% CNC 40 wt% CNC Transmittance (%) Neat PAN-co-MAA CNC-5 CNC-10 CNC-20 CNC-30 CNC-40 Manuscript in progress Wavelength (nm) 16

17 PAN/CNC Film Thermal Stability Composite show higher thermal stability compared to neat PAN and neat CNC <350 C 100 Neat PAN-co-MAA Experimental 40 wt% CNC Rule of Mixture 40 wt% CNC Experimental 100 wt% CNC Experimental 100 Neat PAN-co-MAA Experimental 40 wt% CNC Rule of Mixture 40 wt% CNC Experimental 100 wt% CNC Experimental Weight percent (%) Air Weight percent (%) Nitrogen Temperature ( C) Temperature ( C) Manuscript in progress 17

18 PAN/CNC Fiber Mechanical Properties Addition of 10 wt% CNC lead to a 35% increase in tensile modulus. Precursor Diameter (μm) Tensile Strength (MPa) Tensile Modulus (GPa) PAN 20.1 ± ± ± ± 0.5 PAN/CNC (99/1) 19.2 ± ± ± ± 1.1 PAN/CNC (95/5) 18.3 ± ± ± ±0.5 PAN/CNC (90/10) 19.3 ± ± ± ±0.9 Strain at Failure (%) H. Chang et al., ACS Biomaterials Science and Engineering, (2015) 18

19 PAN/CNC Fiber Dynamic Mechanical Analysis Incorporation of CNC increases the Tg of the PAN, and reduces chain mobility at Tg. 1E10 (d) (c) (b) (a) (a) (b) (c) (d) E' (Pa) (a) PAN fiber (b) PAN/CNC 1 wt % fiber (c) PAN/CNC 5 wt % fiber (d) PAN/CNC 10 wt % fiber Tan (a) PAN fiber (b) PAN/CNC 1 wt % fiber (c) PAN/CNC 5 wt % fiber (d) PAN/CNC 10 wt % fiber 1E Temperatue ( o C) Temperatue ( o C) H. Chang et al., ACS Biomaterials Science and Engineering, (2015) 19

20 Conclusions CNT templating of PAN during carbonization increased the thermal and electrical conductivity with the addition of 1 wt % or less CNT. 30 wt% lignin was incorporated into PAN and made into carbon fiber with no decrease in mechanical properties. CNCs were shown to be better dispersed in a co solvent system compared to single solvent system. Viscosity of PAN/CNC suspension increased with time, possibly due to PAN/CNC interactions. PAN/CNC composites exhibit higher thermal stability than both neat PAN and neat CNC. Incorporation of 10 wt% CNC in PAN fibers increased the tensile modulus by 35%. Higher loadings of CNC in fibers showed increasing Tg and decreasing chain mobility at Tg. 20

21 Acknowledgements Research group lead: Dr. Satish Kumar Research Scientist Dr. Prabhakar Gulgunje Dr. Kishor Gupta Funding agencies DARPA Renewable Bioproducts Institute Air Force Office of Scientific Research Post-doctoral fellow Dr. Sourangsu Sarkar Ph.D. students Amir Davijani Clive Liu Po-Hsiang Wang Huibin Chang Shruti Venkatram Past group members 21

22 Thank you PRESENTED BY Jeffrey Luo Graduate Research Assistant Georgia Institute of Technology 22

23 CNC Dispersion in Co solvent System Branson 3510R MT, 100 W, 42 khz) Hydrodynamic radius (nm) H 2 O-DMF co-solvent H 2 O-DMF co-solvent 60 Pure water CNC concentration (mg/100ml) 23

24 CNC Dispersion TEM Images Water Water DMF (25 75) 24

25 PAN/CNC Film Mechanical Properties 60% increase in tensile modulus with incorporation of 40 wt% CNC Sample Tensile Strength (MPa) Tensile Modulus (GPa) Strain at Failure (%) PAN 62 ± ± ±3.8 PAN/CNC (95/5) 72 ±4 1.9 ± ±2.2 PAN/CNC (90/10) 81 ±6 2.1 ± ±0.7 PAN/CNC (80/20) 86 ±5 2.5 ± ± 0.5 PAN/CNC (70/30) 79 ± ± ± 0.4 PAN/CNC (60/40) 84 ±4 2.9 ± ±

26 PAN/CNC Film Dynamic Mechanical Analysis Storage Modulus (GPa) 1E10 1E9 1E8 Neat PAN-co-MAA CNC-5 CNC-10 CNC-20 CNC-30 CNC-40 Tan Delta Neat PAN-co-MAA CNC-5 CNC-10 CNC-20 CNC-30 CNC Temperature ( C) Temperature ( C) 26

27 PAN/CNC Film Thermal Stability Weight percent (%) Composite show higher thermal stability compared to neat PAN and CNC Increasing CNC loading Neat PAN-co-MAA CNC-5 CNC-10 CNC-20 CNC-30 CNC-40 Neat CNC Weight percent (%) Increasing CNC loading Neat PAN-co-MAA CNC-5 CNC-10 CNC-20 CNC-30 CNC-40 Neat CNC 20 0 Air Temperature ( C) 20 0 Nitrogen Temperature ( C) 27