www.bris.ac.uk/composites

Stimuli-Responsive Polymers for

Multifunctional Composites

Ian Manners

Inorganic, Macromolecular and Materials Chemistry Group

School of Chemistry

Organic Polymers

•cata

lysts

•ele

ctrode m

edia

tors

•photo

nic

mate

rials

•conductive m

ate

rials

•photo

conductive m

ate

rials

•lu

min

escent m

ate

rials

•sensors

•stim

uli

responsiv

e g

els

•m

agnetic m

ate

rials

•fa

brication o

f nanopattern

ed s

urfaces

•hie

rarc

hic

al self-a

ssem

ble

d m

ate

rials

•m

eta

lloenzym

e m

odels

•W

hitte

ll, G

.R. M

anners

, I.

“Metallopolymers -New Multifunctional Materials

”Adv Mater 2007, 19, 3439

•Schubert, U

.S.; M

anners

, I.; N

ew

kom

e, G

.R. (E

ds) AC

S S

ym

posiu

m S

eries (2006)Vol. 9

28

“Metal-Containing and Metallosupramolecular Polymers and Materials

”

Metallopolymers

Metallopolymers --New M

ultifunctional Materials

New M

ultifunctional Materials

Adv. Func. Mater.2002, 12, 415

Air (O

2) Pressure Sensor

•quenching of phosphorescence from excited triplet state

sid

e c

hain

meta

llopoly

mer

Hig

h p

ressure

Low

pre

ssure

-phosphore

scence inte

nsity d

istrib

ution

(fals

e c

olo

r)

dye

dye*

Quenched b

y O

2

Polyferrocenylsilanes (PFSs)

Poly(ferrocenylsilane)

PFS

Fe

Si

Me

Me

n

exam

ple

•Science2001, 294, 1664

main

chain

meta

llopoly

mer

Properties of PFS : Ceramic Precursors

Science, 2000, 287, 1460

> 500°C

PFS

ceramic

> 500°C

, N

2

Ordered Arrays of Magnetic Ceramic Nanorods via Nanoim

print Lithography

AAO

= n

anoporo

us A

nodic

Alu

min

ium

Oxid

e

Patterned M

agneticNanorods

Fe

SiMe

Me

Fe

Si

MeMe

n/2

Fe

SiMe

Me

Fe

Si

MeMe

n/2

Fe

SiMe

Me

Fe

Si

MeMe

n/2

E1/2

(1)

E1/2

(2)

++

+

Properties of PFS -Redox Control of Polymer Polarity

non-polar

polar

oxid

ize

reduce

A PFS gelw

ith a

sm

all

degre

e o

f cro

sslin

kin

g in a

highly polar solvent:

Neutral Fe(II)

Cationic Fe(III) and Neutral Fe(II)

expanded

contracted

SEM of a single scale of a Morpho rhetenor butterfly wing

Chara

cte

rized b

y fix

ed lattic

e s

pacin

g -

Bra

gg / s

top-b

and w

avele

ngth

and c

olo

r is

fix

ed

Natural Photonic Crystals : Opals and Butterfly W

ings

Natural Opals

Tunable lattice spacing = Tunable colour

Redox-Responsive Photonic Crystals Based on PFS Gels

blue

Oxidize or Reduce

Solvent Swollen Gel

red

Working Eletrode

Electrolyte/Solven

t

Modified C

ounter Electrode

Polymer G

el Photonic C

rystal

Broken

Circu

it

Application of a Voltag

e Bias

Positively Polarized W

orking Electrode

Site of Oxidation of PFS

Neg

atively Polarized C

ounter

Swelling of Composite

Upon O

xidation of PFS

Electrochemical Tuning

ITO w

orking electrode

Photonic Ink (P-ink)

Prototype Devices

500

600

700

0

10

20

30

40

50

Reflectivity (%)

Wavele

ngth

(nm

)

initia

l re

flecta

nce

reflecta

nce follo

win

g a

ppl. o

f 1.2

V for 2m

in

reflecta

nce follo

win

g a

ppl. o

f 1.4

V for 2m

in

reflecta

nce follo

win

g a

ppl. o

f 1.6

V for 2m

in

reflecta

nce follo

win

g a

ppl. o

f 1.8

V for 2m

in

Electrochemical Tuning of P-Ink

Num

ber of C

ycle

s

Bragg Peak (nm)

Photonic Crystal Displays using PFS Gels with Redox Tunable Swellability

1-s

ingle

MATE

RIA

L

RG

B +

near-

IR

Using Patterned Electrodes

Opalu

x Inc.

ww

w.o

palu

x.c

om

/

Nature Photonics,2007

1, 468

Features and Advantages of Photonic Ink (P-ink)

1. Full

colo

r dis

pla

y fro

m s

ingle

mate

rial fo

r lo

w m

ate

rials

and p

roduction c

ost.

2. M

eet sig

nage n

eeds in s

ize fro

m s

helf e

dge to h

ighw

ay b

illboard

s.

3. H

igh b

rightn

ess, peak reflectivity u

p to 9

5%

.

4. Low

pow

er consum

ption.

1. Low

voltage a

nd c

urrent during s

witchin

g.

2. M

inim

al pow

er consum

ption w

hen im

age is s

tatic.

5. Sub-s

econd s

witchin

g s

peed.

6. Applic

able

on rig

id o

r flexib

le s

ubstrate

s.

7. Lig

htw

eig

ht, rugged, dura

ble

, and d

am

age tole

rant.

8. C

osts

scale

s o

nly

lin

early w

ith s

ize.

Product under Development -

battery

charg

e indic

ato

r

ww

w.o

palu

x.c

om

Nature Photonics2007, 1, 468

Angew. Chem. Int. Ed.2009,48, 943

Summary

Summary

•Metal Centers can IntroduceInteresting Properties and Functions

-m

ultifunctional com

posites

•Stimuli-Responsive and Functional Materials:

-air p

ressure

sensors

based o

n p

hosphore

scence q

uenchin

g

-pre

curs

ors

to c

era

mic

s c

onta

inin

g m

agnetic a

nd c

ata

lytically

active n

anopartic

les

-re

dox-responsiv

e g

els

for photo

nic

cry

sta

l dis

pla

ys

EPS

RC

, EU

Marie C

urie C

hair, EU

Inte

rnational R

ein

tegra

tion G

rant,

EU

Marie C

urie P

ostd

octo

ral Fello

wship

Pro

gra

m, AW

E, Lanxess,

Spanis

h G

overn

ment PD

F P

rogra

m, D

FG

PD

F P

rogra

m,

Royal Socie

ty W

olfson R

esearc

h M

erit Aw

ard

, N

SER

C P

DF P

rogra

m,

Univ

ers

ity o

f Bristo

l Sta

rt U

p F

unds

FUNDING

COLLABORATIONS

Geoff O

zin

(Toro

nto

)

Mitch W

innik

(Toro

nto

)C

aro

line R

oss (M

IT)

Jennifer Lu (Agile

nt)

Tom

Russell

(U M

ass)

Ric

h S

ponta

k (N

C S

tate

)

ALL M

Y STUDENTS

Thanks for lis

tenin

g !