raman spectroscopy of 3-d printed polymers · pdf fileraman spectroscopy of 3-d printed...

Raman Spectroscopy of 3-D Printed Polymers

Vanessa Espinoza, Erin Wood1 and Angela Hight Walker1

In collaboration with Jonathan Seppala2, Anthony Kotula2, and Kalman Migler2

1

1

2

About Meu Texas Lutheran University

u Rising Senior

u Double major: Chemistry, Physics

u Previous Experience

u National Energy Technology Laboratory (DOE): Summer 2015, Spectroscopic Analysis of Metal Doped Nanoclusters

u TLU: Summer 2014, Biomimetic Modeling of Acireductone Dioxygenase’s Active Site

2https://media.licdn.com/media/p/6/000/1b7/2d5/22ff87d.png ; https://upload.wikimedia.org/wikipedia/en/thumb/2/28/Texas_Lutheran_University.png/220px-Texas_Lutheran_University.png

TLU NIST

u 3-D printing is an additive manufacturing process by which digital 3-D design data is used to build up a component in layers by depositing material.

3

Background-3-D Printing

u 3-D printing parameters

u Material

u Polymers

u Printer Type

u Fused Deposition Modeling

u Shear Rates

u Temperature

Applications are endless!

C. V. Raman1928

phonon!phonon!+

EShift

PhononEmissionStokes

PhononAbsorptionAnti-Stokes

≈

Background-Technique UseduRaman Spectroscopy

uForm of vibrational spectroscopy

uInelastic scattered light

4

ELaser

Elaser - hνvib

ELaser

Raleigh-Elastic Scattering

Raman-Inelastic Scattering

v3v4

v2v1

Eo

Virtual stateE1

StokesAnti-Stokes

5

Background-Technique Usedu Polarized Raman Spectroscopy

u A technique that quantifies alignment of polymer chains

Symmetric CH2 stretch

Asymmetric CH2 stretch

CH2 bend

CH2 twist

x

y

Incident light: X0°

Incident light: Y90°



CCD Collects

Different Combinations

0° XY (cross)

90° YY(parallel)

90° XY (cross)

0° YY(parallel)

6

Background-Technique Usedu Polarized Raman Spectroscopy

u A technique that quantifies alignment of polymer chains

Symmetric CH2 stretch

Asymmetric CH2 stretch

CH2 bend

CH2 twist

x

y





CCD Collects


0° XY (cross)

90° YY(parallel)

90° XY (cross)

0° YY(parallel)

u Acrylonitrile Butadiene Styreneu LEGOs

u Computer keyboards

u Bisphenol-A-polycarbonate u Safety glasses

7http://www.eos.info/additive_manufacturing/for_technology_interested; https://polycraft.utdallas.edu/research/polycraft/images/2/23/ABS-polymer.png;

Background-Polymers Studied

“S”

“A” “B”

ABS

PC

u Acrylonitrile Butadiene Styreneu LEGOs

u Computer keyboards

u Technical Project u Determine qualitative homogeneity of components using Raman

spectroscopy

u Compare experimental results to previously published worku Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Journal of

Applied Polymer Science 133.30 (2016).


1 of 2 Polymers Studied

“S”

“A” “B”

ABS

7

Microtomed Cross-Sectional Area (Top View)Side View

ABS- Terminology

200 µm

100 µm

peakmidpoint

Center to

edge

Mid to MidWeld Zone

Road

u ABSu Determine qualitative homogeneity of components using Raman

spectroscopy

u Compare experimental results to previously published worku Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Journal of

Applied Polymer Science 133.30 (2016).

u BPAPCu Use polarized Raman spectroscopy to analyze alignment of

polymer chains under different conditions

10

Technical Project

https://www.creativemechanisms.com/blog/everything-you-need-to-know-about-abs-plastic; http://pslc.ws/modelgifs/pc.gif

0 1 0 20 30 4 0 500.0

0.1

0.2

0.3

0.4

0.5B/A ABS Inte nsity Ratios

B/A

Ra

tio

Position (cm -1 )0 10 20 30 40 50

0 .0

0 .1

0 .2

0 .3

0 .4

0 .5B/S ABS Internsity Ratios

B/S

Ra

tio

Position (m icrons)

B/A ABS Intensity Ratio B/S ABS Intensity Ratio

Position (microns)

B/S

Rati

o

Position (microns)

B/A

Rati

o

11

ABSHomogeneity

Peak of RoadMidpoint of Road

CS Mid to MidCS Weld Zone

Position B/A B/S

Mean Stnd Dev Mean Stnd Dev

Peak of Road 0.259 0.027 0.363 0.035

Midpoint of Road 0.267 0.022 0.365 0.030

CS Mid to Mid 0.262 0.015 0.373 0.018

CS Weld Zone 0.238 0.014 0.369 0.023

200 µm

100 µm

0.0

0.2

0.4

0.6

0.8

1.0

B /A B/SB /SB/ A

Intens ity Ratio R

atio

s

ABS Scans Position

A rea Ratio Area Ratio Intensity Ratio

ABS Scan Position

Rati

os

0 1 0 20 30 4 0 500.0

0.1

0.2

0.3

0.4

0.5B/A ABS Inte nsity Ratios

B/A

Ra

tio

Position (cm -1 )0 10 20 30 40 50

0 .0

0 .1

0 .2

0 .3

0 .4

0 .5B/S ABS Internsity Ratios

B/S

Ra

tio

Position (m icrons)

B/A ABS Intensity Ratio B/S ABS Intensity Ratio

Position (microns)

B/S

Rati

o

Position (microns)

B/A

Rati

o

12

ABSHomogeneity



Position B/A B/S

Mean Stnd Dev Mean Stnd Dev

Peak of Road 0.259 0.027 0.363 0.035

Midpoint of Road 0.267 0.022 0.365 0.030

CS Mid to Mid 0.262 0.015 0.373 0.018

CS Weld Zone 0.238 0.014 0.369 0.023

200 µm

100 µm

Rati

os

Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Journal of Applied Polymer Science 133.30 (2016). 8

ABS-Homogeneity Comparison with previous work



200 µm

100 µm

0.0

0.2

0.4

0.6

0.8

1.0

B /A B/SB /SB/ A

Intens ity Ratio

Rat

ios

ABS Sc ans Position


ABS Scan Position

Rati

os

160 0 220 0 2 4000

10 00

20 00

30 00ABS Ra man SpectrumC

ou

nts

Raman Shift (cm -1 )

ABS Raman Spectrum Co

unts

Raman Shift (cm-1)

u Looked at multiple scans from line map

u Curve fit of peaks

u Peaks focused on in ABS Raman spectrum

u A ~ 2238 cm-1

u B ~ 1667 cm-1

u S ~ 1604 cm-1

u Relative ratios

u Area

u Intensity

14

ABSHomogeneity



200µm

100µm

0.0

0.2

0.4

0.6

0.8

1.0

B /A B/SB /SB/ A

Intens ity Ratio R

atio

s

ABS Scans Position


ABS Scan Position

Rati

os

15

ABSComparison with previous work

u Raman spectroscopy mapping of interfacial areas revealed ~30% less B/S and B/A ratios with respect to analysis of the build surfaces.

u Peak selection

u Scanning direction

u Printing parameters

u Printing temperature

u 230°C vs 203°C

u Printers used

u Maker Bot vs Stratasys Fortus

u Dimensions of samples

90 0 950 100 0 1 05 0 1 55 0 16 00 165 0 1 700 17 500

10 00

20 00

30 00

40 00

50 00

60 00

ABS Ram an Spectrum of S tyrene Peaks

Co

un

ts


ABS Raman Spectrum of Styrene Peaks

Coun

ts

Raman Shift (cm-1)Cole, Daniel P., et al. "Interfacial mechanical behavior of 3D printed ABS."Journal of Applied Polymer Science 133.30 (2016).

u Bisphenol-A-polycarbonate u Safety glasses

u Technical Project u Use polarized Raman spectroscopy to analyze

alignment of polymer chains under different conditions


PC

50 0 10 00 150 0 200 0 2 500 30 000

100 00

200 00

300 00

400 00

500 00PC Ram an Spectrum

Co

un

ts


PC Raman Spectrum

Coun

ts

Raman Shift (cm-1)

2 of 2 Polymers Studied

u Samples of interest:

u Extruded filament

u Hand-drawn extruded filament

u Neat filament

u 100 mm/sec printed sample

u 10 mm/sec printed sample

17

Polycarbonate (PC)Sampling Parameters

18

PolycarbonatePeak Assigning

50 0 55 0 60 0 6 50 15 00 1 550 160 0 165 0 17 00

No

rma

lize

d C

ou

nts

Raman Shift (cm -1 ) 10

Polycarbonate-Phenyl Rings

Phenyl rings

Nor

mal

ized

Cou

nts

Normalized Raman Spectra

Raman Shift (cm-1)

CrossParallel


0° XY (cross)

90° YY(parallel)

90° XY (cross)

0° YY(parallel)

1 000 125 0 15 00

B

A

11

Polycarbonate-Differences in SpectraN

orm

aliz

ed C

ount

s


Raman Shift (cm-1)

CrossParallel

2 800 290 0 300 0 31 00 32 00

B

A


Nor

mal

ized

Cou

nts

Raman Shift (cm-1)

12

Polycarbonate-Sample Orientations

5 00 1 000 15 00 2 00 0 25 00 30 00

Samp le Orientation Raman Spectras

Off

se

t N

orm

aliz

ed

Co

un

ts

Ram an Shift (cm - 1)

Raman Spectra of Sample Orientations

Off

set

Nor

mal

ized

Cou

nts

Raman Shift (cm-1)

x

y






0° XY (cross)

90° YY(parallel)

90° XY (cross)

0° YY(parallel)

CrossParallel

2 800 290 0 300 0 31 00 32 00

B

A 22

Polycarbonate- CH stretching

CH3 stretch

C=C-H stretch

Nor

mal

ized

Cou

nts


Raman Shift (cm-1)

CrossParallel

u Homogeneity in ABS sample

u Polarized Raman spectroscopy shows to be useful with understanding of polymer chain alignment

13

Conclusion

Further Experimentationu Further explore the properties of polycarbonate

u Understanding crystallization in semi-crystalline materials

u Polycaprolactone (PCL)

u Polylactic acid (PLA)

u Further explore the properties of BPAPC

u Understanding crystallization in semi-crystalline materials

u Polycaprolactone (PCL)

u Polylactic acid (PLA)

24

Further Experimentation

u American Institute of Physics

u Society of Physics Students

u Angela Hight Walker and the Hight Walker Group

u Family and Friends

u Fellow Interns

14

Acknowledgements+ Adam

Questions?

26

15

15 00 155 0 1 600 16 50 170 0 1 75 0

Ram an Spectra of Pure Poly mer Sam ples

Off

se

t C

ou

nts


u Reasons for difficulty

u Different isomers exist

u Low signal to noise

u Overlap with other peaks

27

ABSParameter Optimization

cis-1,4-polybutadienetrans-1,4-polybutadiene1,2-polybutadiene

polystyrenepolyacrylonitrile

28

5 00 1 000 15 00 2 00 0 25 00 30 00

Samp le Orientation Raman Spectras

Off

se

t N

orm

aliz

ed

Co

un

ts

Ram an Shift (cm - 1)

29

500 10 00 15 00 20 00 25 00 3 000

1 00

2 00

3 00

4 00

5 00Polar ized Ram an of Polycarbonate 10 m m /s

No

rma

lize

d C

ou

nts

W avenumbers (cm -1)

Pa ralle l Pe rpe nd icu lar

1 60 4 -C=C-

2 87 2.1 1

2 912.52 2972.73 CH 3 as sym

3 0 7 3 .2 2 =C-H

3063.35 =C-H3069.52 =C-H

7 06 .37 6 OO P =C-H

829.80 5 OO P = C-H

73 4.507 O OP?

8 88.431 c ar bonate grou p

1 0 01 . 29 IP = C -H1 0 2 2 .0 9

IP

1444.36 CH3 def 1465.6

CH 3 def

C -O -C s tr 108 0-13 10

1 772 .0 1 C=O63 6. 48 2 Aro m ring d ef576.126

30

50 0 10 00 1 500 20 00

1 00

2 00Polar ized Ram an of Polycarbonate 10 m m /s

No

rma

lize

d C

ou

nts

W avenumbers (cm -1)

Pa ralle l Pe rpe nd icu lar

1 60 4 -C=C-

7 06 .3 76 O OP =C-H

82 9.8 05 O OP =C -H

73 4.507 O OP?

888 .431 c ar bonate g roup

1 0 0 1 .2 9 IP = C - H

10 2 2 .0 9 IP

14 44.36 C H

3 def

1465 .6 CH 3 de f

C -O -C s tr 108 0-13 10

17 72.01 C =O

63 6.4 82 Arom ring d ef

576.126

raman spectroscopy of 3-d printed polymers · pdf fileraman spectroscopy of 3-d printed...

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