3D Optical Printing of Piezoelectric Nanoparticle-Polymer Composite ...
3D Optical Printing of Piezoelectric Nanoparticle-Polymer Composite Materials Kanguk Kim1†, Wei Zhu2†, Xin Qu2, Chase Aaronson2, William R. McCall2, Shaochen Chen1,2, and Donald J. Sirbuly1,2*
1
Materials Science and Engineering, University of California, San Diego, La Jolla, California 92093, United States 2 Department of NanoEngineering, University of California, San Diego, La Jolla, California 92093, United States †
These authors contributed equally to this work.
*
E-mail: [email protected]
Contents 1. Powder X-ray diffraction of the as-made BTO nanoparticles (Figure S1) 2. FTIR spectra of the TMSPM-grafted BTO nanoparticles (Figure S2) 3. UV-Vis spectra of PEGDA-BTO solutions (Figure S3) 4. Force sensor characterization (Figure S4) 5. Charge amplifier set-up (Figure S5) 6. Voltage response of a honeycomb array (Figure S6)
1
30
40
50
60
70
(103)
(212) (300)
(202)
(112) (102)
(002)
(111)
20
[1]
BT-NP 86nm
(001)
Intensity [a.u.]
(101)
BaTiO3 P4mm
80
2degree] Figure S1. XRD pattern of the as-made BTO nanoparticles and a reference BaTiO3 pattern.[1] The XRD spectra indicate that the nanoparticles have a strong tetragonal phase given their c/a ratio of 1.007. The spectra were recorded using a Bruker D8 X-ray diffractometer
[1] Evans, H. T., An X-ray diffraction study of tetragonal barium titanate. Acta Cryst. 1961, 14, 1019-1026.
2
BaTiO3 BaTiO3
Intensity [a.u.]
with TMSPM TMSPM
C=O
-OH -CCH3 4000
3500
3000
2500
2000
1500
1000
-1
Wavenumber [cm ] Figure S2. The chemical structure of TMSPM (top left) and FTIR spectra of pure TMSPM (blue), as-made BTO nanoparticles (black), and TMSPM-grafted BTO nanoparticles (red). The bands at 2862-2882 cm-1 are attributed to C-CH3 and O-CH3 groups and the band at 1720 cm-1 is attributed to the C=O group. The broad peak centered at 3500 cm-1 is attributed to hydroxyl groups on the BTO nanoparticles which are present both in the as-made and TMSPM-modified samples. The samples were washed with copious amounts of ethanol and water prior to taking spectra and provide good evidence (along with the enhanced piezoelectric properties) that the TMSPM is grafted to the surface of the BTO nanoparticles. The spectra were recorded using a Spectrum Two spectrometer (Perkin Elmer).
3
100
Transmittance (%)
80
pure PEGDA PEGDA+1% BTO PEGDA+5% BTO PEGDA+10% BTO
60 40 20 0 300
400
500
600
700
Wavelength (nm) Figure S3. UV-Vis spectra of pure PEDGA (green) and PEGDA/BTO composite solutions; 1 % (black), 5 % (red), and 10% (blue). The transmittance is directly related to the BTO loading fraction and shows higher transmission at longer wavelength. The spectra were recorded using a Lambda 35 UV-Vis system (Perkin Elmer).
4
S (a) A sch hematic of the t FlexiForcce® sensor (Tekscan) ccircuit and (bb) the calibrration Figure S4. curve. Kn nown forcess were placed d on the sen nsor using ann Instron 59882 material ttesting apparratus. A piece of PDMS was w placed on o the forcee sensor to pprotect the surface of tthe sensor annd to distributee the load equally. How wever, it was found thatt there are m minimal diffferences bettween similar lo oads with different contact areas. The T output vvoltage of thhe sensor coould be tuneed by changing g the supply voltage and d the feedbaack resistor, R1. The caapacitor, C1, was used aas the bypass capacitor. Un nder the mo ost sensitive set-up (-5 V supplied and R1 = 10 kthe sensor shows a linear l relatio onship with respect r to load above 2 N and an expponential rellation below w 2 N.
5
S A schem matic of the charge amplifier used iin the piezoeelectric expeeriments. Chharge Figure S5. generated d from the piezoelectriic polymer is transferrred to the rreference caapacitor, C1, and producess an output voltage, v Vout, that is equaal to the volttage across C1. The Vout can be expressed as Vc = -Q - generated/C1. In the experiments a 100 1 pF capaacitor (and 220 Mfeedbback resistorr, R1) was used d as the refeerence capaccitor allowin ng the piezoeelectric coeffficient, d33, to be calcuulated from d33 = Vout × 100 0 pF/Fapplied.
6
800
Voltage (mV)
600 400 200 0 -200 -400 -0.4
-0.2
0.0
0.2
0.4
Time (s) Figure S6. Voltage response of a 5% BTO loaded PEGDA honeycomb array (similar structure to Figure 2d) fabricated by DPP.
7
1
Materials Science and Engineering, University of California, San Diego, La Jolla, California 92093, United States 2 Department of NanoEngineering, University of California, San Diego, La Jolla, California 92093, United States †
These authors contributed equally to this work.
*
E-mail: [email protected]
Contents 1. Powder X-ray diffraction of the as-made BTO nanoparticles (Figure S1) 2. FTIR spectra of the TMSPM-grafted BTO nanoparticles (Figure S2) 3. UV-Vis spectra of PEGDA-BTO solutions (Figure S3) 4. Force sensor characterization (Figure S4) 5. Charge amplifier set-up (Figure S5) 6. Voltage response of a honeycomb array (Figure S6)
1
30
40
50
60
70
(103)
(212) (300)
(202)
(112) (102)
(002)
(111)
20
[1]
BT-NP 86nm
(001)
Intensity [a.u.]
(101)
BaTiO3 P4mm
80
2degree] Figure S1. XRD pattern of the as-made BTO nanoparticles and a reference BaTiO3 pattern.[1] The XRD spectra indicate that the nanoparticles have a strong tetragonal phase given their c/a ratio of 1.007. The spectra were recorded using a Bruker D8 X-ray diffractometer
[1] Evans, H. T., An X-ray diffraction study of tetragonal barium titanate. Acta Cryst. 1961, 14, 1019-1026.
2
BaTiO3 BaTiO3
Intensity [a.u.]
with TMSPM TMSPM
C=O
-OH -CCH3 4000
3500
3000
2500
2000
1500
1000
-1
Wavenumber [cm ] Figure S2. The chemical structure of TMSPM (top left) and FTIR spectra of pure TMSPM (blue), as-made BTO nanoparticles (black), and TMSPM-grafted BTO nanoparticles (red). The bands at 2862-2882 cm-1 are attributed to C-CH3 and O-CH3 groups and the band at 1720 cm-1 is attributed to the C=O group. The broad peak centered at 3500 cm-1 is attributed to hydroxyl groups on the BTO nanoparticles which are present both in the as-made and TMSPM-modified samples. The samples were washed with copious amounts of ethanol and water prior to taking spectra and provide good evidence (along with the enhanced piezoelectric properties) that the TMSPM is grafted to the surface of the BTO nanoparticles. The spectra were recorded using a Spectrum Two spectrometer (Perkin Elmer).
3
100
Transmittance (%)
80
pure PEGDA PEGDA+1% BTO PEGDA+5% BTO PEGDA+10% BTO
60 40 20 0 300
400
500
600
700
Wavelength (nm) Figure S3. UV-Vis spectra of pure PEDGA (green) and PEGDA/BTO composite solutions; 1 % (black), 5 % (red), and 10% (blue). The transmittance is directly related to the BTO loading fraction and shows higher transmission at longer wavelength. The spectra were recorded using a Lambda 35 UV-Vis system (Perkin Elmer).
4
S (a) A sch hematic of the t FlexiForcce® sensor (Tekscan) ccircuit and (bb) the calibrration Figure S4. curve. Kn nown forcess were placed d on the sen nsor using ann Instron 59882 material ttesting apparratus. A piece of PDMS was w placed on o the forcee sensor to pprotect the surface of tthe sensor annd to distributee the load equally. How wever, it was found thatt there are m minimal diffferences bettween similar lo oads with different contact areas. The T output vvoltage of thhe sensor coould be tuneed by changing g the supply voltage and d the feedbaack resistor, R1. The caapacitor, C1, was used aas the bypass capacitor. Un nder the mo ost sensitive set-up (-5 V supplied and R1 = 10 kthe sensor shows a linear l relatio onship with respect r to load above 2 N and an expponential rellation below w 2 N.
5
S A schem matic of the charge amplifier used iin the piezoeelectric expeeriments. Chharge Figure S5. generated d from the piezoelectriic polymer is transferrred to the rreference caapacitor, C1, and producess an output voltage, v Vout, that is equaal to the volttage across C1. The Vout can be expressed as Vc = -Q - generated/C1. In the experiments a 100 1 pF capaacitor (and 220 Mfeedbback resistorr, R1) was used d as the refeerence capaccitor allowin ng the piezoeelectric coeffficient, d33, to be calcuulated from d33 = Vout × 100 0 pF/Fapplied.
6
800
Voltage (mV)
600 400 200 0 -200 -400 -0.4
-0.2
0.0
0.2
0.4
Time (s) Figure S6. Voltage response of a 5% BTO loaded PEGDA honeycomb array (similar structure to Figure 2d) fabricated by DPP.
7
