Raman Spectroscopy of 3-D Printed Polymers

Transcription

1 Raman Spectroscopy of 3-D Printed Polymers Vanessa Espinoza, Erin Wood 1 and Angela Hight Walker 1 In collaboration with Jonathan Seppala 2, Anthony Kotla 2, and Kalman Migler

2 Abot Me Texas Ltheran University Rising Senior Doble major: Chemistry, Physics Previos Experience National Energy Technology Laboratory (DOE): Smmer 2015, Spectroscopic Analysis of Metal Doped Nanoclsters TLU: Smmer 2014, Biomimetic Modeling of Aciredctone Dioxygenase s Active Site TLU NIST ; 2

3 Backgrond-3-D Printing 3-D printing is an additive manfactring process by which digital 3-D design data is sed to bild p a component in layers by depositing material. 3-D printing parameters Material Polymers Applications are endless! Printer Type Fsed Deposition Modeling Shear Rates Temperatre 3

4 Backgrond-Techniqe Used Raman Spectroscopy Form of vibrational spectroscopy Inelastic Raman-Inelastic Scattering ELaser Elaser - hνvib scattered light ELaser Raleigh-Elastic Scattering E1 Virtal state Stokes Anti-Stokes C. V. Raman 1928 Eo v4 v3 v2 v1 Phonon Absorption Anti-Stokes Phonon Emission Stokes EShift +! phonon! phonon 4

5 Backgrond-Techniqe Used CH 2 twist Polarized Raman Spectroscopy A techniqe that qantifies alignment of polymer chains CH 2 bend Incident light: X 0 Incident light: Y 90 Incident light: X 90 Incident light: Y 0 Different Combinations 0 XY (cross) Asymmetric CH 2 stretch y CCD Collects 90 YY(parallel) 90 XY (cross) x 0 YY(parallel) Symmetric CH 2 stretch 5

6 Backgrond-Techniqe Used CH 2 twist Polarized Raman Spectroscopy A techniqe that qantifies alignment of polymer chains CH 2 bend Incident light: X 0 Incident light: Y 90 Incident light: X 90 Incident light: Y 0 Different Combinations 0 XY (cross) Asymmetric CH 2 stretch y CCD Collects 90 YY(parallel) 90 XY (cross) x 0 YY(parallel) Symmetric CH 2 stretch 6

7 Backgrond-Polymers Stdied Acrylonitrile Btadiene Styrene LEGOs ABS Compter keyboards A B S Bisphenol-A-polycarbonate Safety glasses PC 7

8 1 of 2 Polymers Stdied Acrylonitrile Btadiene Styrene LEGOs Compter keyboards A ABS B S Technical Project Determine qalitative homogeneity of components sing Raman spectroscopy Compare experimental reslts to previosly pblished work Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Jornal of Applied Polymer Science (2016)

9 ABS- Terminology Side View Microtomed Cross-Sectional Area (Top View) Weld Zone Mid to Mid midpoint peak Center to edge Road 200 µm 100 µm 7

10 Technical Project ABS Determine qalitative homogeneity of components sing Raman spectroscopy Compare experimental reslts to previosly pblished work Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Jornal of Applied Polymer Science (2016). BPAPC Use polarized Raman spectroscopy to analyze alignment of polymer chains nder different conditions

11 ABS 0.5 Homogeneity 1.0 Area Area Ratio Ratio B/A B/A ABS ABS Intensity Ratios 0.5 Intensity Ratio Intensity Ratio B/S ABS Intensity Ratio B/S ABS Internsity Ratios 0.8 B/A Ratio Ratios B/S Ratio B/S Ratio Peak of Road Midpoint of Road CS Mid to Mid CS Weld Zone Position (microns) (cm -1 ) Position (microns) Position B/A B/S 0.0 B/A MeanB/S Stnd B/A Dev Mean B/S Stnd Dev Peak of Road ABS Scans Position Midpoint of Road CS Mid to Mid µm 100 µm CS Weld Zone

12 ABS Homogeneity 0.5 B/A B/A ABS ABS Intensity Ratios 0.5 B/S ABS Intensity Ratio B/S ABS Internsity Ratios B/A Ratio Ratios B/S Ratio B/S Ratio Peak of Road Midpoint of Road CS Mid to Mid CS Weld Zone Position (microns) (cm -1 ) Position (microns) Position B/A B/S Mean Stnd Dev Mean Stnd Dev Peak of Road Midpoint of Road CS Mid to Mid µm 100 µm CS Weld Zone

13 ABS-Homogeneity Raman Comparison Spectrm with 3000 previos work Looked at mltiple scans from line map 1.0 Area Ratio Area Ratio Intensity Intensity Ratio Ratio Crve fit of peaks Ratios 0.8 Conts Peaks focsed on in ABS Raman spectrm A ~ 2238 cm -1 B ~ 1667 cm -1 S ~ 1604 cm B/A B/S Raman B/A Shift (cm B/S -1-1 ) ABS Scan Position ABS Scans Position Peak of Road Midpoint of Road Relative ratios CS Mid to Mid CS Weld Zone Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Jornal of Applied Polymer Science (2016). 8 Area Intensity 200 µm 100 µm

14 ABS Homogeneity 1.0 Area Area Ratio Ratio Intensity Ratio 0.8 Ratios Peak of Road Midpoint of Road CS Mid to Mid CS Weld Zone B/A B/S B/A B/S ABS Scans Position 100µm 200µm 14

15 ABS Comparison with previos work Raman spectroscopy mapping of interfacial areas revealed ~30% less B/S and B/A ratios with respect to analysis of the bild srfaces. Peak selection ABS ABS Raman Raman Spectrm of of Styrene Peaks Peaks Scanning direction Printing parameters Printing temperatre 230 C vs 203 C Printers sed Maker Bot vs Stratasys Forts Dimensions of samples Conts Conts Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Jornal of Applied Polymer Science (2016) Raman Raman Shift Shift (cm -1-1 ) 15

16 2 of 2 Polymers Stdied Bisphenol-A-polycarbonate Safety glasses PC PC Raman Spectrm PC Raman Spectrm Technical Project Use polarized Raman spectroscopy to analyze alignment of polymer chains nder different conditions Conts Conts Raman Shift (cm -1 ) -1 ) 9

17 Polycarbonate (PC) Sampling Parameters Samples of interest: Extrded filament Hand-drawn extrded filament Neat filament 100 mm/sec printed sample 10 mm/sec printed sample 17

18 Polycarbonate Peak Assigning 18

19 Polycarbonate-Phenyl Rings Normalized Raman Spectra Normalized Conts Normalized Conts Cross Parallel Phenyl rings Different Combinations 0 XY (cross) 90 YY(parallel) 90 XY (cross) 0 YY(parallel) Raman Shift Shift (cm -1-1 )) 10

20 Polycarbonate-Differences in Spectra Normalized Raman Spectra Normalized Raman Spectra Normalized Conts B B Normalized Conts Cross Parallel Raman Shift A (cm -1 ) Raman A Shift (cm -1 ) 11

21 Polycarbonate-Sample Orientations Raman Sample Spectra Orientation of Sample Raman Orientations Spectras Incident light: X 0 Incident light: Y 90 Offset Normalized Conts Offset Normalized Conts y Incident light: X 90 Incident light: Y 0 Different Combinations 0 XY (cross) 90 YY(parallel) 90 XY (cross) 0 YY(parallel) x Raman Shift (cm -1 ) Cross Parallel 12

22 Polycarbonate- CH stretching Normalized Raman Spectra C=C-H stretch Normalized Conts B CH 3 stretch Cross Parallel Raman Shift (cm -1 ) A 22

23 Conclsion Homogeneity in ABS sample Polarized Raman spectroscopy shows to be sefl with nderstanding of polymer chain alignment Frther Experimentation Frther explore the properties of polycarbonate Understanding crystallization in semi-crystalline materials Polycaprolactone (PCL) Polylactic acid (PLA) 13

24 Frther Experimentation Frther explore the properties of BPAPC Understanding crystallization in semi-crystalline materials Polycaprolactone (PCL) Polylactic acid (PLA) 24

25 Acknowledgements American Institte of Physics + Adam Society of Physics Stdents Angela Hight Walker and the Hight Walker Grop Family and Friends Fellow Interns 14

26 Qestions? 26 15

27 ABS Parameter Optimization Reasons for difficlty Different isomers exist Low signal to noise Raman Spectra of Pre Polymer Samples Overlap with other peaks Offset Conts cis-1,4-polybtadiene trans-1,4-polybtadiene 1,2-polybtadiene polystyrene polyacrylonitrile Raman Shift (cm -1 ) 27

28 Sample Orientation Raman Spectras Offset Normalized Conts Raman Shift (cm -1 ) 28

29 500 Polarized Raman of Polycarbonate 10 mm/s Parallel Perpendiclar =C-H Normalized Conts C -O -C s tr CH 3 as sym =C-H =C-H c ar bonate gro p C=C OO P =C-H Aro m ring d ef OOP? IP OO P = C-H =C-H IP CH 3 def CH 3 def C=O Wavenmbers (cm -1 ) 29

30 200 Polarized Raman of Polycarbonate 10 mm/s Parallel Perpendiclar Normalized Conts OOP =C-H C -O -C s tr c ar bonate g rop C=C Arom ring d ef OOP? OOP =C-H IP =C-H IP CH 3 def CH 3 de f C =O Wavenmbers (cm -1 ) 30