Polymer Nanocomposite: SNU Chem. Eng. Polymer Materials Lab

4.
Polymer Nanocomposite
Polymer Materials Lab. SNU Chem. Eng.

 Introduction
 Nanocomposites
Heterogeneous materials in which the characteristic length scale of the
filler material is in the nanometer range
• Efficiency increase by its large surface-area-to-volume ratios
• Certain properties can be modified due to the small size of the
filler, while not affecting other properties
• Dynamic response to external stimuli
 Polymer-matrix nanocomposites
• Enhancement of mechanical, optical, thermal, fire-retardant, ablative
properties, gas-transport properties
• Precise control of the dispersed inclusions is necessary
block copolymers(BCPs) as scaffolds materials

 Characteristic differences between nanometer-sized
and traditional filler composites
(1) Ultra-low percolation thresholds(~1 vol%)

(2) particle-particle correlation arising at low concentrations(<0.1vol%)
(3) Large particle-number densities of up to ~1020 cm-3
(4) Extensive interfacial area per volume of particles(~107cm2cm-3)
(5) Short particle-particle distances
(6) Comparable length scales between the particle sizes,
the distances between the particles,
the typical relaxation volume of a polymer chain.

20/93

30/93

 Block Copolymer-based Nanocomposite Materials
 Types of BCP depending on the dimensionality of the inclusion

Zero-dimensional (0D ; dot)
One-dimensional (1D ; tube)
Two-dimensional (2D ; sheet)
 Synthetic approaches
• The particles are synthesized in situ within the fixed BCP matrix
; depending on the reaction and diffusion kinetics of the growing
crystals
• The nanocomposite is fabricated by co-assembly of the BCP and
nanoparticles that is synthesized ex situ.
; depending on the equilibrium thermodynamics

 BCP-based nanocomposite materials 40/93
 Symmetry considerations
• Surface modification to
stabilize nanoparticles against
aggregation
• The particle has to fit into the
space provided by the favorable
block domains
• (+) ; compatibility of a particle’s
point symmetry group within the
minority component of a
respective BCP,
(-) ; incompatibility
• L=lamella, DG=double gyroid,
C=cylindrical, S=spherical

 In-situ synthesis
“nanoreactor scheme”
• 2D hexagonal patterns of metal particles in a BCP matrix
• Infilterating the hydrophilic domains of spherical PS-b-PAA copolymer
with a silver salt that was reduced
Y. Boontongkong, R.E.Cohen, Macromolecules, 2002, 35,3647

 In-situ synthesis
reaction-diffusion controlled nucleation and growth process

• synthesis of cobalt oxide nanoclusters stabilized by PMMA chains
• initiated by the formation of small clusters that act as nucleation sites,
and deplete reactant from the surrounding polymer matrix
• the aggregation and stabilizations occur only after the metallomers
have reached a critical size and a distinct surface structure
S. King, K. Hyunh, R. Tannenbaum, J. Phys. Chem. B 2003, 107, 12097.

 Ex-situ synthesis
 Control of the length scale and the spatial organization of

block copolymer morphologies
Control of the location of nanoscopic inclusion using entropic effects
• Gold nanocrystals(d=3.5 nm) are found to segregate
between the PS and PEP domains.
• The larger silica nanocrystals(d=21.5 nm) are mostly

located ar the center of the PEP domains
In ternary systems consisting of block copolymer and
two different-sized nanocrystal, the distinct
morphological types are conserved, resulting in
autonomous separation and organization
M. R. Bockstaller, Y. Lapetnikov, S. Margel, E. L. Thomas, JACS, 2003, 125, 5276.

 Ex-situ synthesis
 Control of the length scale and the spatial organization of

block copolymer morphologies
For large particles, the decrease

in conformational entropy of the
respective polymer subchains
upon particle sequestration
is dominant,
whereas for smaller particles,
the decrease in entropy is
outweighed by the particle’s
translational entropy
d/L=0.06 for gold
d/L=0.26 for silica
d: particle
L: domain dimension
M. R. Bockstaller, Y. Lapetnikov, S. Margel, E. L. Thomas, JACS, 2003, 125, 5276.

Mesoporous carbons and their derivatives

Brief introduction
 Mesoporous carbons
Adv. Mater. 2006, 18, 2073..
 Mesoporous carbon are considered to have a pore in the range of 2 and 50

nm, and a fascinating properties including chemical inertness, mechanical
stability, uniform pore size, high surface area, and large pore volume.
 The synthetic route for mesoporous carbon largely depends on hard

template method.
 For the improved performance, chemical modification should be introduced

into mesoporous carbon with low activity.

Experimental
 Schematic diagram

Silica-FeCl3 and Silica-PPy
 TEM images
Silica-FeCl3 nanocomposite Silica-PPy nanocomposite
 Densely filled structure of silica-PPy nanocomposite implied that VDP

of pyrrole monomer successfully took place.

N-doped MC
 TEM images
N-doped MC22 N-doped MC12 N-doped MC7
 Colloidal template method provided a 3-dimensionally interconnected and

disordered pore structure.
 The controlled pore diameter was achieved by suggested method.

N-doped MC 50/93
 Pore characteristics
Nitrogen adsorption Pore size distribution
Type IV
hysteresis
 The N-doped MCs exhibited type IV hysteresis behavior and tunable pore
diameter in BET analysis, which was same with TEM result.

N-doped MC
 Nitrogen characteristics
XPS C1s XPS N1s
C-N/C-O bond C-C bond

(285.8 eV) (284.5 eV)
Pyrrolic-N
Pyridinic-N (398.6 eV)
(400.3 eV)
 The N-doped MC showed the increased ratio C-N and C-C and large
nitrogen species with pyridinic and pyrrolic-nitrogen.
 The high nitrogen amount (8.4 wt.%) was confirmed by XPS analysis.

N-doped MC
 Carbonaceous characteristics
Raman spectroscopy HR-TEM image
IG/Id = 1.23
IG/Id = 1.11
IG/Id = 0.96 10 nm
Graphitic layer
 Under low carbonization temperature, N-doped MC showed the

semicrystalline graphitic structure due to iron complexes doped in PPy.

N-doped MC
 Electrochemical application (EDLC electrode)
CS= 153.2 F g-1 CS= 175.8 F g-1
CS= 102.4 F g-1 CS= 162.7 F g-1
 Heteroatom of N-doped MC endowed the improved wettability with

electrolyte and pseudo-capacitance.
 Large surface area of N-doped MC increased the specific capacitance (CS),

which was accordance with general explanation.
MC-PPy nanocomposite

 Pore characteristics
Nitrogen adsorption Pore size distribution
 The textual property (type IV hysteresis) was retained after impregnation of

polypyrrole.
 The pore size systematically decreased with increasing PPy loading: 20.3 (31
wt. %), 17.3 nm (43 wt. %), and 15.5 nm (55.5 wt. %).
 TEM images
Pristine MC MC-PPy1
 The gradual increment in pore
wall thickness proved the
successful impregnation of
polypyrrole layer onto the pore
surface of mesoporous carbon.
MC-PPy2 MC-PPy3
 The tailored amount of PPy

was introduced into MC
without blockage even at high
PPy loading.

 MC12-PPy nanocomposite
TEM image Pore size distribution
9.1 nm
 The impregnation of polymer layer was successfully applied to MC with

small pore diameter as shown in TEM and BET analysis.

 MC7-PPy nanocomposite
5.6 nm
 The MC7-PPy nanocomposite clearly exhibited the PPy layer on pore

surface and resulting decrement of pore size from 7 to 5.6 nm.

 It was clear that specific capacitance (CS) of MC-PPy nanocomposite

increased with increasing PPy amount and deviated rectangular
morphology was shown.

MC-PPy nanocomposite 60/93
 Relation between PPy and capacitance

Function of PPy amount on CS Mechanism
Carbon
PPy layer Electron
Electron Acceptor
CS = 233.6 F g-1
donor
1) Charge-transfer complex
2) Pseudo-capacitance
3) Surface area
 While the added PPy layer enhanced capacitance due to charge-transfer

complex and pseudo-capacitance, the decreased surface area provided the
saturated value.
CS = 274.5 F g-1
CS = 238.9 F g-1
 It was demonstrated that introduction of PPy layer enhanced the performance

of EDLC electrode and MC-PPy nanocomposite could be applied as electrode
materials.

 Removal of Heavy metal ions

Hg2+ adsorption Filter application
Tetraphenylporohinesulfonate (TPPS)
 The mercury ion-adsorptive performance of MC-PPy was four times

compared to pristine carbon materials and was checked by using mercury
ion detective molecule (TPPS).
 Removal of Heavy metal ions

Pb2+ adsorption Ag+ adsorption
 MC-PPy nanocomposites exhibited superior metal ion uptake toward lead and
silver ion and the nitrogen of PPy layer played a crucial role in improved
performance.

MC-PT nanocomposite
 MC-PT nanocomposite
16.2 nm
 In additional to PPy, polythiophene (PT) was impregnated onto pore

surface and selected for investigation of preferential adsorption behavior.

MC-Polymer nanocomposites
 Selective adsorption behavior

Metal uptake Mechanism
Hard metal
Soft metal
 The selective adsorption behavior was ascribed to different atoms:

nitrogen and sulfur of PPy and PT, respectively.

85/102
Silica-titania hollow nanoparticles and

the electrorheological properties
of their suspensions

Brief introduction
 Hollow nanoparticles
Science 1998, 282, 1111. Langmuir 2008, 24, 12134.
 The void space of hollow nanostructures have led to modulate index, lower
density, increase active area for catalysis, and expand the field of imaging
markers.
 The spontaneous reactions (Ostwald ripening, Kirkendall effect, and reversible

sol-gel reaction) have emerged as a novel route for hollow nanoparticles.

Brief introduction
 Electrorheological fluids (ER fluids)
Soft Matter 2009, 5,1562.
 ER fluids consisted of electrically polarizable particles dispersed in insulating

oils and showed field-induced rheological property.
 The reversible ER activity has been applied into engineering application such as
torque transducers, vibration attenuations, control systems.
 In spite of the broad interest, applications have been hampered by the

weakness of the ER effect.

Silica-titania core-shell NPs
?
Sonication
 The increased diameter confirmed the introduction of titania shell layer

onto the surface of silica colloidal nanoparticle.

CSNPs and HNPs 70/93
 TEM images
CSNP20H CSNP45H CSNP90H CSNP95L
HNP25H HNP50H HNP100H HNP100L
** CSNPa-b and HNPa-b represent silica/titania core/shell nanoparticles and silica-titania based hollow nanoparticles with
different diameter (a) and titania amount (b).

CSNPs and HNPs
 Atomic distribution (EDX and EELS mapping)

CSNP45H HNP50H
 In the case of CSNP, the

distinct two areas (silica and
titania) and core-shell
structure were observed
 HNP showed the silica and

titania coexistence and valley
like structure and implied the
silica-titania mixed shell
layer.

HNPs
 Plausible mechanism
 Evolution of hollow structure was

due to sonication-induced sever
reaction condition, reversible sol-
gel reaction and different etching
reactivity.
 Under sonication, high intensity

energy droved in cavity between
silica and titania of partially silica
etched CSNPs.

HNPs
 Porous structure
Nitrogen adsorption
Vtot = 1.05 cm3 g-1 Vtot = 0.94 cm3 g-1
Vtot = 0.32cm3 g-1 Vtot = 1.17 cm3 g-1
 HNPs had the obvious hysteresis loop and increased pore volume,
suggesting the void of hollow structure.

HNPs
 The interface between silica and titania

XPS O1S IR spectroscopy
Macrocyclic
siloxane
(1100 cm-1)
Si-O-Ti
Si-O-Si
(531.8 eV) Si-O-Ti
Ti-O-Ti Linear
(530.2 eV) siloxane
(1020 cm-1)
 The formation of linear siloxane and decrement of macrocyclic siloxane

implied that microstructure of silica regions were highly confined into
titania shell layer.
HNPs
 Anti-pairing and polarization
 The suggested microstructure of HNPs showed the increased interface

between silica and titania.
 Especially, increased interface decreased the anti-pairing which might be
negative factor for ER activity. The interface and anti-pairing played a key
factor in high ER performance of HNP.

CSNP & HNP-based suspensions
 Yield stress & applied electrical field

CSNP-based suspensions HNP-based suspensions
102 kPa 300 kPa
 All suspensions had a linear tendency of applied electrical field, which was
governed by saturation polarization model.
 The size and structure-dependent yield stress was observed.

 Formation of fibril structure

Optical images TEM image
 In a few seconds, the randomly dispersed ER materials transformed into

net-like and dense fibril structure.
 The resulting fibril structure provided high viscosity and yield stress of
suspensions under applied electrical field.
 ER behavior
CSNP25H-suspensions HNP25H-suspensions
Bingham fluid
Bingham fluid
Newtonian fluid Newtonian fluid
 Electrostatic interaction between ER materials and hydrodynamic force

from shear flow continuously competed and induced the alternation of
Bingham fluid and Newtonian fluid.
 ER behavior
Reversibility Volume fraction
 Yield stress increased and decreased with electrical on and off and this
reversibility suggested the possibility for practical use.
 More particles easily formed the dense fibril structure, high electrical
interaction, and yield stress.
HNP/SDBS-based suspensions
 Wettability
NP filled
tube
Oil
 The HNP/SDBS suspensions exhibited large slope and increased wettability due
to oleophilic part of surfactant, SDBS on the surface of HNPs.

 Relation of SDBS and yield stress

Electrical field SDBS amount
489 kPa
 The added SDBS prevented highly aggregated nanostructure and provided

molecular dipole between oil and nanoparticles.
 Excess amount of SDBS increased the gap width, resulting in drop of
electrostatic interaction.
 ER behavior
Shear stress Volumetric variation
Bingham fluid
Newtonian fluid
 HNP/SDBS-based suspensions showed the general characteristics as shown in

the case of CSNP and HNP: Alternation of Bingham fluid and Newtonian fluid,
and volumetric dependency.

 Sedimentation
Oil a
ER
Fluid b Sedimentation ratio =
(b/(a+b))
 In the case of modified HNPs, enhanced antisedimentation (94 % after 30

days) was observed owing to oleophilicity from SDBS and low density from
hollow nanostructure.

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4.

Polymer Materials Lab. SNU Chem. Eng.

Polymer Materials Lab. SNU Chem. Eng.

(1) Ultra-low percolation thresholds(~1 vol%)

Polymer Materials Lab. SNU Chem. Eng.

Polymer Materials Lab. SNU Chem. Eng.

Polymer Materials Lab. SNU Chem. Eng.

 Types of BCP depending on the dimensionality of the inclusion

Polymer Materials Lab. SNU Chem. Eng.

Polymer Materials Lab. SNU Chem. Eng.

Y. Boontongkong, R.E.Cohen, Macromolecules, 2002, 35,3647

Polymer Materials Lab. SNU Chem. Eng.

reaction-diffusion controlled nucleation and growth process

S. King, K. Hyunh, R. Tannenbaum, J. Phys. Chem. B 2003, 107, 12097.

Polymer Materials Lab. SNU Chem. Eng.

 Control of the length scale and the spatial organization of

• The larger silica nanocrystals(d=21.5 nm) are mostly

M. R. Bockstaller, Y. Lapetnikov, S. Margel, E. L. Thomas, JACS, 2003, 125, 5276.

Polymer Materials Lab. SNU Chem. Eng.

 Control of the length scale and the spatial organization of

For large particles, the decrease

Polymer Materials Lab. SNU Chem. Eng.

Polymer Materials Lab. SNU Chem. Eng.

Adv. Mater. 2006, 18, 2073..

 Mesoporous carbon are considered to have a pore in the range of 2 and 50

 The synthetic route for mesoporous carbon largely depends on hard

 For the improved performance, chemical modification should be introduced

Polymer Materials Lab. SNU Chem. Eng.

Polymer Materials Lab. SNU Chem. Eng.

 Densely filled structure of silica-PPy nanocomposite implied that VDP

Polymer Materials Lab. SNU Chem. Eng.

 Colloidal template method provided a 3-dimensionally interconnected and

Polymer Materials Lab. SNU Chem. Eng.

Polymer Materials Lab. SNU Chem. Eng.

C-N/C-O bond C-C bond

Polymer Materials Lab. SNU Chem. Eng.

 Under low carbonization temperature, N-doped MC showed the

Polymer Materials Lab. SNU Chem. Eng.

 Electrochemical application (EDLC electrode)

CS= 153.2 F g-1 CS= 175.8 F g-1

CS= 102.4 F g-1 CS= 162.7 F g-1

 Heteroatom of N-doped MC endowed the improved wettability with

 Large surface area of N-doped MC increased the specific capacitance (CS),

Polymer Materials Lab. SNU Chem. Eng.

 The textual property (type IV hysteresis) was retained after impregnation of

 The tailored amount of PPy

Polymer Materials Lab. SNU Chem. Eng.

 The impregnation of polymer layer was successfully applied to MC with

Polymer Materials Lab. SNU Chem. Eng.

 The MC7-PPy nanocomposite clearly exhibited the PPy layer on pore

Polymer Materials Lab. SNU Chem. Eng.

 Electrochemical application (EDLC electrode)

 It was clear that specific capacitance (CS) of MC-PPy nanocomposite

Polymer Materials Lab. SNU Chem. Eng.

 Relation between PPy and capacitance

 While the added PPy layer enhanced capacitance due to charge-transfer

 Electrochemical application (EDLC electrode)

 It was demonstrated that introduction of PPy layer enhanced the performance

Polymer Materials Lab. SNU Chem. Eng.

 Removal of Heavy metal ions

 The mercury ion-adsorptive performance of MC-PPy was four times

 Removal of Heavy metal ions