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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°
Incident light: X90°
Incident light: Y0°
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
Incident light: X0°
Incident light: Y90°
Incident light: X90°
Incident light: Y0°
CCD Collects
Different Combinations
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).
6http://www.eos.info/additive_manufacturing/for_technology_interested; https://polycraft.utdallas.edu/research/polycraft/images/2/23/ABS-polymer.png;
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
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
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
Peak of RoadMidpoint of Road
CS Mid to MidCS Weld Zone
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
A rea Ratio Area Ratio Intensity Ratio
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
Peak of RoadMidpoint of Road
CS Mid to MidCS Weld Zone
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
A rea Ratio Area Ratio Intensity Ratio
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
Raman Shift (cm -1 )
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
9http://www.eos.info/additive_manufacturing/for_technology_interested; https://polycraft.utdallas.edu/research/polycraft/images/2/23/ABS-polymer.png;
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
Raman Shift (cm -1 )
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
Different Combinations
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
Normalized Raman Spectra
Raman Shift (cm-1)
CrossParallel
2 800 290 0 300 0 31 00 32 00
B
A
Normalized Raman Spectra
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
Incident light: X0°
Incident light: Y90°
Incident light: X90°
Incident light: Y0°
Different Combinations
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
Normalized Raman Spectra
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
Raman Shift (cm -1 )
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
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