Synthesis of Functional Polymer

Coatings via Roll-to-Roll Vapor

Deposition

Malancha Gupta
Mork Department of Chemical Engineering
and Materials Science
University of Southern California
Initiated Chemical Vapor Deposition (iCVD)

• One-step, solventless polymerization process

• Surface tension effects associated with liquid
processing do not exist in the vapor phase
• Coating process is substrate-independent
• Responsive (light, heat, pH), hydrophilic, and
hydrophobic coatings can be made

Uncoated fabric Coated fabric

O’Shaughnessy et al., T.P. Martin and K.K. Gleason, Biomaterials, 2007.
Biomacromolecules, 2007
iCVD Mechanism
monomer
CH CH
3 3

CH C O O C CH
3 3

CH CH
3 3

tert-butyl peroxide

I-I 2I.

MMM I. IMMM.
Substrate
Chiller

Classical Free Radical Polymerization

Initiation: I-I 2I.
I. + M I-M.
Propagation: I-M. +(n-1)M I-Mn.
Termination: I-Mn.+ I-Mm. I-Mm+n-I
I-Mn. + I. I-Mn-I
Kinetics Associated with iCVD
150
QM=0.3 sccm Substrate Temperature Series
QI=0.8 sccm
rate (nm/min)

100 P=100 mTorr Substrate Temp Mw Polydispersity

(oC)
44 177300 2.27
50
49 114300 2.63
54 42800 2.01
0
310 315 320 325 330 335 Monomer Partial Pressure Series
substrate temperature (K)
400 PM/Psat Mw Polydispersity
350 Ts=44oC 0.50 127800 1.89
300 QI=0.8 sccm
Rate (nm/min)

P=100 mTorr 0.45 109300 1.91

250
200 0.38 91100 1.91
150
100 Deposition rate and molecular weight increase
50 with decreasing substrate temperature and
0 increasing monomer partial pressure
0.05 0.1 0.15 0.2 0.25 0.3
P /P
m sat M. Gupta and K.K. Gleason, Langmuir, 2006
Functional iCVD Polymers

n n n n
poly(glycidyl poly(propargyl poly(furfuryl poly(pentafluorophenyl
methacrylate) methacrylate) methacrylate) methacrylate)

n n n n

poly(o-nitrobenzyl poly(N-isopropyl poly(1H,1H,2H,2H- poly(2-hydroxyethyl

methacrylate) acrylamide) perfluorodecyl methacrylate)
acrylate)
Conformal Coatings
spin-coating iCVD

Tenhaeff et al., Adv. Funct. Mater., 2008.

PPCVD iCVD

5 W continuous
plasma dep rate ~
10 nm/min ton = 20 ms
iCVD dep rate ~ toff=20000 ms
300 nm/min P=40 W

monomer
Baxamusa et al., Thin Solid Films, 2009.
 Areas of Interest
Elastomeric and Porous Materials
Lab on a Chip, 2011, 11, 3049. Soft Matter, 2011, 7, 2428.
Langmuir, 2011, 27, 10634.
ACS Applied Materials & Interfaces, 2011, 3, 4201.
ACS Applied Materials & Interfaces, 2012, 4, 6911.
Ionic Liquids
Macromolecules, 2011, 44, 2653, Macromolecules, 2012, 45, 165.
Langmuir, 2012, 28, 10276, Langmuir, 2013, 29, 1640,
Macromolecules, 2014, 47, 6657, Langmuir, 2015, 31, 7999,
Langmuir, 2016, 32, 11014, Langmuir, 2017, 33, 7701.
Langmuir, 2013, 29, 10448,
Macromolecules, 2013, 46, 6852.
Biomedical Implants
Journal of Micromechanics and Microengineering, 2014, 24, 065003.
Journal of Vacuum Science & Technology A, 2016, 34, 041403.
Beilstein Journal of Nanotechnology, 2017, 8, 1629.
Polymer Membranes
Macromolecules, 2013, 46, 2976,
ACS Applied Materials & Interfaces, 2013, 5, 9714,
Macromolecular Materials and Engineering, 2016, 4, 371,
Macromolecular Materials and Engineering, 2016, 301, 1037,
Polymer, 2017, 126, 463.
 Roll-to-Roll Module

Width
Feed
Motor
roll

Rolling direction Outlet

Precursor to
Length

inlet Primary pump

deposition
zone

Receiver
Motor
roll

Heated
filaments

3 m-long roll of 5 cm-wide paper was placed into the reactor and continuously coated

The paper traveled through the primary deposition (12.5 cm long) at an average
velocity of 2.5 cm/min
Industrial & Engineering Chemistry Research 2018, 57, 11675.
Fluorinated Coatings

1H,1H,2H,2H-Perfluorodecyl acrylate Flat surface

O q=120o
H2C CH C OCH2CH2(CF2)7CF3 g ~ 9.3 mN/m

Roll-to-Roll
Uncoated Stationary
Coated Paper
Paper Coated Paper
(1.5 m)
Completely 142º ± 2º 141º ± 3º
wets
Top

144º ± 3º 143º ± 3º
Bottom
Uniformity of Polymer Coating along Length
Atomic Composition Contact Angle

• Atomic compositions along the length (3 m) on both sides show no significant

variation, which indicates the uniformity of the PPFDA.
• Contact angles on the top and bottom sides are comparable, demonstrating that
the coating has penetrated through the thickness of the paper.
Uniformity of Polymer Coating across Width

Atomic Composition Contact Angle

100 100
F
90 90 O
152
C
80 80
150
70 70
148

Contact Angle (°)

% Composition

60 60 0.1 m Top
146 0.1 m Bottom
50 50 1.5 m Top
144
1.5 m Bottom
40 40 142 2.9 m Top
2.9 m Bottom
30 30 140
20 20 138
10 10 136
0 1 2 3 4 5
0 0 Distance (cm)
cm 5 cm 8 cm 2c
m cm 8 cm
0.2 2. 4. 0. 2.5 4.
Coated Top Coated Bottom

Comparisons of the atomic compositions across the width (5 cm) on both sides show
no significant variation.
Hydrophobicity

Roll-to-Roll Coated
Uncoated Paper
Paper (1.5 m)

Top

100 µm 100 µm

Bottom

100 µm 100 µm

1 cm
Slippery Liquid-Infused Porous Surfaces (SLIPS)

Water Isopropanol Chloroform

0s 1s 8s 0s 4s 8s 0s 1s 2s

5 mm 5 mm 5 mm

• Whereas the PPFDA-coated paper is hydrophobic (repels water), the SLIPS

material is omniphobic (repels polar and nonpolar liquids)
• The coated paper is infused with perfluorinated liquid (Krytox)
• For our SLIPS material at a 15° tilt, water, isopropanol, and chloroform all rolled
off within seconds, whereas the latter two solvents do not roll off paper coated
with PPFDA
Cross-linked Coatings for Separations

Uncoated xPMAA Coated Paper

Paper

PMAA

Eluent Flow
Direction of
Mixture of
Dyes

Crystal
Ponceau S
Violet
(anionic)
(cationic)

For 1 cm-wide channels, we can fabricate 300 microfluidic channels in a single deposition
Patterning Porous Substrates

Electron beam lithography Capillary force lithography Colloidal lithography

Mao et al., J. Vac. Sci. Technol., B, 2004 Im et al., J. Am. Chem. Soc., 2008 Trujillo et al., Thin Solid Films, 2009

Patterning onto porous substrates using a physical mask

iCVD is not a line-of-sight process

 Light-Sensitive Polymers
Uncoated Coated

100 µm 100 µm

O1s C1s O1s C1s

N1s

After exposure, paper Dry patterned Patterned paper

is soaked in pH 8 buffer paper with dye
Mask covering
coated paper

1 cm

1 cm 1 cm 1 cm

Retention of fluid indicates successful patterning in 3-dimensions

Soft Matter, 2011, 7, 2428.
 Photoinitiated CVD Process

UV-light (254 nm) UV-light (254 nm)

Adsorb BP Flow
BP H
BP to off
surface EGDA
BP H
EGDA
BP BP BP BP Graft
EGDA
Parylene C Parylene C

TBP
O
Start
Heated Filament wire
iCVD VP VP
reaction
with EGDA
Solvent
desired TBPO TBPO
wash
gPVP
monomer
(UV off) gPEGDA
gPEGDA
Parylene C Parylene C

M. M. De Luna, B. Chen, L. C. Bradley, R. Bhandia, M. Gupta, J. Vac. Sci. &

Tech. A. (2016) 34, 041403.
Coating 3-D Printed Objects

Multiple objects can be coated at once

Uncoated ABS Coated with PHEMA-co-PEGDA Coated with PPFDA

Beilstein Journal of Nanotechnology, 2017, 8, 1629.

 Vapor Phase Deposition Regimes
Monomer
above its
saturation
Typical conditions used in
pressure?
vapor phase polymerization
No Yes
Monomer remains in the
vapor phase Thin Film Substrate
temperature 500 µm
Deposition rates: typically below
10-100 nm/min monomer Monomer deposition and
freezing polymerization occur
point? simultaneously

No Yes Deposition rates: up to

40 µm/min
100 µm Nonporous Porous
Film Film Macromolecules 2013

Monomer condensation and

polymerization occur simultaneously

Deposition rates: up to 600 nm/min

10 µm
Tao et al. Langmuir 2012
 Mechanism
• Use thermoelectric cooler
• Simultaneous solid monomer deposition and polymerization
• Large-scale pores form during deposition by void space between microstructures
• Small-scale pores form during sublimation of solid monomer

Large-scale pores
Monomer Deposition and Polymerization
Deposition Partial Polymerization
Monomer
Removal

Monomer Polymer Free Radical Species

Small-scale pores

Resultant Structures
200 µm

Large-scale pores
20 µm
Small-scale pores

Macromolecules, 2013, 46, 2976.

Fluorinated iCVD Coating

After sublimation, the surface of the porous structures can be modified

using the traditional iCVD process.

1H,1H,2H,2H-Perfluorodecyl acrylate Flat surface

O q=120o
H2C CH C OCH2CH2(CF2)7CF3 g ~ 9.3 mN/m

CA=130° Thickness=418 ± 25 µm
Porous-on-Porous Materials

Bottom-up process allows for the production of “porous-on-porous” materials

PMAA

Cellulose 100 µm ponceau S

1 mm
crystal violet

ACS Applied Materials and Interfaces, 2013, 5 , 9714.

Acknowledgements

NSF EFRI