>> Focus on sustainability,innovation and international

From Smart, Self-healing to Bio-inspired and

Biomimetic Materials: R&D in China

Tongxiang Fan

Shanghai Jiaotong University,

Shanghai, China.

Email: txfan@sjtu.edu.cn

Advanced Materials Seminar,

Hague, the Netherland,

December 12th, 2012

Contents

>> Focus on sustainability,innovation and international

2

Introduction1

Typical R&D in China2

Research in My Group3

>> Focus on sustainability,innovation and international

3

Introduction

Optical fiber Gel

1991

NiTi Shape Memory Alloy

Piezoceramics

2012

History of Smart Materials in China

11

44

1. Electrorheological /Magnetorheological fluid（（（（ERF/BRF））））

2. piezoelectric ceramics

3. electrochromic mateials

22

33

4. photochromic materials

Inorganic non-metallic intelligent material

Types

ERF：A suspension. liquid (electric field)solid

BRF： A suspension.is high permeability rate, low hysteresis

of the tiny magnetic particles soft and non-derivative magnetic

liquid mixture of suspension

A ceramics materials. It has piezoelectric effect.

electric energymechanical energy

Under the action of electric current(electric field) ,it can

produce absorption or scatter of light.

The reversible change of color

It reversibly change their absororption spectra that are their

color and related optical properties in response to incident

optical illumination

Electrorheological flflflfluid materials

1.Coprecipitation method

JOURNAL OF APPLIED PHYSICS 107, 093507-(1~5),2010

Department of Physics and Institute of Nano Science and Technology, The Hong

Kong University of Science and Technology

barium chloride

MCNTs

titanium tetrachloride

oxalic acid

coprecipitated

65 °C

colloidal solsfiltrated dry

Silicone oilsdry

molecular

sieves

GER fluids

Characterization of rheological properties

2. Sedimentation property

a/(a+b)

FIG.1. (a)Sedimentation ratio , methyl terminated silicone

oil(20cSt),concentration of 5.0. (b)Images of samples ( 12.5

days after preparation)

sedimentation ratio:

FIG.2. (a)SEM images

(b)microstructures

structures in the two cases

FIG. 3. FT-IR spectra

3.Yield stress

FIG. 4. Zero-field

viscosity plotted The

Concentration is1.0

FIG.5. Measured

GER effect. square

pulse with a

power-on time of

t=50 s, shown in

the inset

FIG. 6. Shear stress

plotted(MCNTs mass

fraction of 0.49%, The

Concentration is1.0

)

FIG. 7. Shear stress of

MCNT-BTRU

nanoparticles

(0.49%,25 cSt, 0.25)

Piezoelectric ceramics material

JOURNAL OF APPLIED PHYSICS 111, 124113-(1~5),2012

Department of Physics, Center for Condensed Matter Science and Technology, Harbin Institute of

Technology

FIG. 1. (a) XRD patterns of(1-

x)BNT-xBC ceramics,(b) the

detailed XRD patterns ，the

rhombohedral-tetragonal

MPB can be determined to

locate near x=0.025~0.035.

TABLE 1. Lattice parameters of the (1-x)BNT-xBC system.

FIG. 4. (a) P-E hysteresis loops of (1-x)BNT-xBC ceramics at room

temperature and (b) Ps, Pr, and Ec as functions of x.

FIG. 5. Bipolar S-E curves of the

poled ceramics.

FIG. 6. Composition-dependent

d33 and kt for the (1-x)BNT-xBC

ceramics.

FIG. 7. Temperature dependences of

poled relative dielectric constant and loss

tangent for (1-x)BNT-xBC ceramics.

Conventional solid state reaction method

(1-x)Bi0.5Na0.5TiO3-xBiCoO3

BiO3, Na2CO3, TiO2, Co2O3

Fig.1 One bending and unbending cycle

after irradiation by UV/visible light (25 ℃).

Photoinduced Deformation of Crosslinked Liquid-Crystalline Polymer Film

Trans-to-cis photoisomerization of

azobenzene moieties.

Reduction in orientation order of CLCP

mesogens along CNT-aligned direction.

Anisotropic contraction in the surface layer.

Fig.2 Chemical structures and properties of

the two monomers and crosslinker.

Anisotropic bending of the composite film.

Sis-to-trans photoisomerization of

azobenzene moieties.

Initial morphology

Deformation Mechanism:

Initial morphology

UV

Visible light

Table 1: Mechanical properties of the CLCP/CNT

composite film

Fig.3 Preparation of an oriented CLCP/CNT

nanocomposite film in four steps.

Preparation:

Step 1. A CNT array was grown on silicon by

chemical vapor deposition.

Step 2. Uniform CNT sheets were pulled out of

the array by dry spinning and stabilized on

glass substrates.

Step 3. An LC cell was made of two

CNT-sheet-covered glass slides with

the CNT sheet inside.

Step 4. A molten mixture of A11AB6, A9Bz9,

and C9A(molar ratio 1:1:3) containing 1 mol%

photoinitiator was injected into the LC cell at

90℃ and then slowly cooled to a

polymerization temperature of 77 ℃ at a rate

of 0.1 ℃ /min.

Step 5. The CLCP/CNT composite film was

obtained after photopolymerization at a

wavelength of 547 nm under a 500 W high-

pressure mercury lamp through a glass filter

for 2 h.

W. Wang, etc. Angew. Chem. Int. Ed. 2012, 51, 4644-4647.

Department of Material Science, Fudan University.

Scheme 1. a)Working principle of self-healing

superhydrophobic coatings

Self-healing Superhydrophobic Coatings

Fig.1 Porous and hierarchical structures

Self-healing process:

Preparation. Fabricate superhydrophobic

coatings which have micro- and nanoscaled

hierarchical structures through chemical vapor

deposition (CVD) of a fluoroalkylsilane.

1. The porous polymer coating with micro- and

nanoscaled hierarchical structures can

preserve an abundance of healing agent units

of reacted fluoroalkylsilane.

2. The top fluoroalkylsilane layer is decomposed

and the coating loses its superhydrophobicity.

3. The preserved healing agents can migrate to the

coating surface and heal the superhydrophobicity.

b) Chemical structure of sulfonated poly-(ether

ether ketone) (SPEEK).

Fig.4 a)X-ray photoelectron spectra and b)EDX

spectra of the as-prepared superhydrophobic

coating.

Fig.2 Changes of Contact Angle (a,b)

in reversible transition and effect of

humidity(c).

Fig.3 a) Top-view SEM image of the

scratched coating. b) Enlarged SEM

image of the scratches in (a) (marked

with an arrow). c,d) Wet-ting

characterization of the scratched coating

before (c) and after self-healing (d).

Y. Li, etc. Angew. Chem. Int. Ed. 2010, 49, 6129-6133.

State Key Laboratory of Supramolecular Structure and

Materials College of Chemistry, Jilin University

Excellent Self-healing Supramolecular Gels

Achievement 1: Stimuli-responsive

Achievement 2: Rapid self-healing

10.0mM 1 and 36.0mM 2(1:1 molar ratio) + DB24C8/DBAS Gel 4

Gel 5

mixed in

chloroform/acetonitrile (v/v=1:1)

1. heating for 30 days in chloroform/acetonitrile(v/v=1:1)

2. stirring for another 45 days at 25 ℃℃℃℃

M. Zhang, etc. Angew. Chem. Int. Ed. 2012, 51,7011-7015.

Department of Chemistry, Zhejiang University.

Gel SolAdd base (TEA)

Add acid (TFA)

Mechanism of Gel 4: reversible host–guest interactions.

Mechanism of Gel 5: the destruction and reformation of

electrostatic and hydrogen-bonding interactions

10.0mM 1 and 36.0mM 3(1:1 molar ratio) + DB24C8/DBAS

SJTU(shanghai jiaotong University): In 1896, an

imperial edict issued by Emperor Guangxu, established

Nanyang Public School in Shanghai.

SJTU(shanghai jiaotong University): In 1896, an

imperial edict issued by Emperor Guangxu, established

Nanyang Public School in Shanghai.

About SJTU and SKL MMCs

SJTU Today:-31 schools/departments-63 undergraduate programs-250 MS programs-203 Ph.D. programs-28 post-doctorate programs-11 state key laboratories and national engineering research centers.

SJTU Today:-31 schools/departments-63 undergraduate programs-250 MS programs-203 Ph.D. programs-28 post-doctorate programs-11 state key laboratories and national engineering research centers.

SKL MMCs:State Key Lab of Metal Composites,Set up in 1986 by MOST of China, focusing on metal, polymer, ceramics and their composites;Aim: to promote fundamental and applied research in China.

Research Funding of SKL MMCs:2007: 41million RMB ($ 5.72 million)2008: 48million RMB ($ 6.86 million)2009: 54 million RNB ($ 7.8 million)

Central

Government55%55%

Local

Government

10%10%

Enterprise29%29%

International

6%6%

New policy: 2008-2012: 50 million RMB ($ 7.2million) directly from central government

In 2011

Hierarchical

Multi-scales

Order, disorder

Abundance

ZnO

ZrO2

TiO2

Solar cell

WO3

SnO2

ZnSCdS

Ag Au

…???…

Filter Sensor

Purifier

Photocatalyst

Shielding

H2 ProductionPainting

New applications

Bio-inspired & Biomimetic Material

Two kinds of colors account for the butterfly wing colorization:

pigmentary color and

structural color

Why butterfly wing?

pigmentary color structural color

Butterfly is one of the most beautiful species on the planet, the beauty and variety of butterfly wings can hardly be matched by any other organisms in the natural world.

Butterfly wings demonstrate brilliant colors due to wonderful skills of light

manipulation intrinsically originated from their elaborate architectures.

For some such as solar cells and photocatalysts and bio-sensor, their inner structures

play dominant role in the working efficiencies.

Butterfly wings demonstrate brilliant colors due to wonderful skills of light

manipulation intrinsically originated from their elaborate architectures.

For some such as solar cells and photocatalysts and bio-sensor, their inner structures

play dominant role in the working efficiencies.

Butterfly: inspiration for new Technology

Solar heaters

Broadband reflection / whiteness

Dye-sensitized Solar cells

iridescence

Antireflection/blackness

Solar cells/ photocatalystsT.X. Fan et al. Energy Environ. Sci., 2012, DOI:10.1039/C2EE03595B

第16页

Prototype 1: Solar Cells Anode inspired by Butterfly Wings

300 400 500 600 700 800

Wavelength (nm)

FTO substrate Anatase film

Ab

sorp

tio

n (

a.u

.)

SCS titania replica film

QHS titania replica film CRS titania replica film

Scales with quasi honeycomb structure can absorb more sunlight that makes butterfly wings rise temperature more quickly.This research provides a new prototype and methodology for designing and manufacturing high efficiency solar cells .

Research progress of super black material:

2002 NiP alloy film

2008 Carbon nanotubes film

This research Amorphous carbon film

Super black

materialAbsorption Thickness

Ni P alloy 99.6% 3030µµmm

carbon

nanotubes 99.9% >30 >30 µµmm

Inverse V-

type a-C99% 11µµmm

Inspired by the anti-reflection structure in black

butterfly wings,coupling of hierarchical structure of

butterfly and amorphous carbon, only 1µm in

thickness, within visible range (380 ~

795nm),absorption is higher than 99% while

reflectance is lower than 1%

Prototype 2: Super black & ultrathin carbon inspired by butterfly wing

Inverse V-type anti-reflection in butterfly wing Inverse V-type amorphous carbon film

Reflectance & transmission spectrum of inverse V-type amorphous carbon film, flat plate

amorphous carbon film and general glassy carbon

Reflectance of inverse V-type a-C is less than 1% ,which is 1/13 of that in flat plate a-C and 1/8 of that in standard black glassy carbon .By introducing inverse V-type anti-reflection stucture of butterfly wings to general amorphous carbon , Super black and ultrathin properties can be achieved, which could be used to optics device and sensor detector.

Prototype 2: Super black & ultrathin carbon inspired by butterfly wing

Hierarchical structure of butterfly wings is

beneficial for light harvesting.

TiO2 photocatalyst with butterfly wings strurcture TiO2-Au-CdS with butterfly wing structure combined with

artificial Z scheme photosynthesis system

Light harvesting computational simulation of

anti-reflection structure of butterfly wing

Prototype 3: Photocatalyst with hierarchical structure inspired by butterfly wings: Light harvesting and water splitting

Artificial Z scheme photocatalysts with the hierarchical structure of butterfly wings.

Light harvesting efficiency in the spectral range of 220nm to 380nm is increased by 30%. Compared with the normal TiO2 photocatalyst, TiO2 with the hierarchical structure of butterfly wings has a 7 times enhancement in the efficiency of H2 production from water splitting. This provides new inspiration for design and preparation of highly

efficient solar system and realization of artificial photosynthesis.

light harvesting propertiesH2 production from water splitting

Prototype 4: Biosensor inspired from Butterfly Wing

Natural Euploea mulciber

Fig. Comparison of Raman signals from R6G on three Ag SERSdiagnostic substrates. R6G concentrations: c) 10-10m; d) 10-11m;Data from top to bottom were collected on Ag butterfly, commercialSERS substrate and Ag film

electrochemical sensor

Morph butterfly wing Scale

Voltammetry simulation results for planar, planar+ridge, butterffly wing

scale architecture indicate enhanced electrochemical efficiency for

butterfly wing scale architecture

Experimental results for ferro/ferricyanide

redox couple on flat-carbon and butterfly

scale architectured carbon electrode

Synthesize metal scales (Au, Pt,

Ag) with dendritic hierarchical

architecture as biosensors

Better water supply means better photosynthesis！！！！

Light CO2

Photosynthesis

H2O

Transpiration

Upper epidermis

Lower epidermis

Vein

Mesophyll

StomaCO2H2O

Gas exchange

Photosynthesis and Transpiration are coupled!!

Better water transport system

Inspired by nature leaves

Better thermal management system

Inspired by leaves

nutrition distribution system with

microvascular networks Inspired by leaves

channel Porous matrix

High heat

Conductivity material

Low heat

Conductivity material

High heat

Conductivity material

Low heat

Conductivity material

Nutrition

inlet

Nutrition

outletchannel Tissue(cells)

Prototype 5: High performance thermal-management and self –healing materials with microvascular networks inspired by green leaf

Naturalprototype

Porous metal foam (Al, Cu)with hierarchical pore structure

Micro-architectured high performancethermal-management material

(CNT/Metal (Cu, Al) etc

Self-healing materials with microvascular networks for bio-application

� Toyota Automobile, Japan� Hitachi Chemical, Japan, � DOW Chemistry ,USA� Schneider electric, France� Mogan Crucible, UK� Alcan Company, Canada� Dynax Company, Japan

� Cambridge University, UK� Osaka University, Japan� ETH, Swiss� Cardiff University, UK� NIMS, Japan� Troyes university, France� University of California, Davis� 。。。。。。。。。。。。。。。。。。。。。。。。

International Cooperation with SKL MMCs

Joint lab

Academic

23

Some ideas about International R&D Collaborations

� To Bridge the gap between Academic and Industry;

� To transfer some natural prototypes to Industry;

� Learning from nature is timeless and some prototypes from the nature were set up and the secrets behind them were revealed in the past, it is time to transfer the academic to the industry.

� Joint Lab or Collaboration R&D works to be expected focusing on one or some of following:

� high performance Micro-architectured thermal-management material;

� Self-healing materials with microvascular networks for bio-application;

� Bio-sensor R &D;

� Multifunctional Porous metal foam with hierarchical structure;

� Energy Materials;

>> Focus on sustainability,innovation and international

24

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internet: www.IAnetwerk.nl

telephone: + 31 88 602 8237

e-mail: ianetwerk@agentschapnl.nl

or contact this speaker directly:

internet: http://smse.sjtu.edu.cn/en/jiaogongdenglu.asp?id=9

telephone: +86-21-54747779

e-mail: txfan@sjtu.edu.cn