Post on 06-May-2015
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Advanced Materials
High Tc SuperconductorsGMR materialsNegative thermal expansion SupercapacitorsThermoelectricsPorous materialsSolid oxide Fuel cell (SOFC)Organic-inorganic hybrid materialsFullerenesNano Materials
Advanced or Smart BiomaterialsBiodegradable Advanced MaterialsSelf-assembled Materials
Future of Material Science :
Nanostructured materials for technologies in 2015 and beyond
Professor A K GanguliDepartment of Chemistry
Indian Institute of Technology Delhi New Delhi 110016
ashok@chemistry.iitd.ac.in
March 9, Bangalore, EmTech India 2010
E.U
USA
Japan
China Rest of world
Global Government Funding
12000 million dollars
2600 million dollars
NANOTECHNOLOGY
Large industry currently supports about half of the R&D in U.S_ $2 billion per yr.
CHINA
Russia<1% to 23%
2004 2009
3% to 10%
INDIA less than 1 %
J. Nanoparticle Res. (2010)
Global Nanotech Funds
• Materials : Controlled Synthesis
• Scale up
• Patterning large scale nanostructures
• contacts, system design
• self- assembly
Organized colloidal aggregates
Reverse - micelles as Nano - reactor
• Monodispersed water droplets• Inhibits the growth and aggregation of grains• Easy control of size and shape of the aqueous coreGanguli et al , Chem Soc Rev ( 2010)
Electroceramics Catalysts magnetics, catalysts
Photocatalysts
Toxin traps
Batteries
BaTiO3 MnC2O4 MnO, Mn2O3
Mn3O4
CdS @ TiO2
Ag@TiO2
Co
Ba2TiO4 FeC2O4 Fe2O3 , Fe3O4 CdS @ SiO2 Cu
SrTiO3 CoC2O4 CoO, Co3O4 NiS @ TiO2 Ni
Sr2TiO4 NiC2O4 NiO NiS @ SiO2 Cu-Ni
PbTiO3 CuC2O4 CuO NiOx@TiO2 Co-Ni
BaZrO3 ZnC2O4 ZnO NiOx@SiO2 Co-Cu
SrZrO3 CdC2O4 SnO2 GMR materials
Magnetic recording
Mn-Ni
PbZrO3 Ce2(C2O4)3 ZrO2 LaMnO3 Hard coatings
Fe2(C2H4C2O
4)3
CeO2 La.67Sr.33MnO3 LaB6
NaTaO3 CoC2H4C2O4 La.67Ca.33MnO3 NbB2
SrTa2O6 CuC2H4C2O4 CrB2
Variety of nanomaterials
NaNbO3
Hollow TiO2 via Ostwald Ripening
J. Phys. Chem. B, 2004, 108, 3492
Digestive Ripening
1. Journal of Nanoparticle Research 2000, 2, 157–1642. J. Am. Chem. Soc., 2002, 124, 2305-2311
Controlling size and shape
Controlling shape
CTAB/1-butanol/Isooctane TX-100/1-hexanol/cyclohexane Tergitol/1-octanol/cyclohexane
NiC2O4.2H2O
Ganguli et al, J. Phys. Chem. C 2008, 112, 12610–12615.
NiO
20 nm 10 nm
25 nm
100nm
Silica nanoparticles on copper succinate nanorods100 nm
silica nanoparticles coated with aminoacid.
By reverse micellesCommercially available NANO -
SiO2
SiO2
Aparna Ganguly et al
IITD
Silica particles (40 nm) :
Aparna et al, Journal of ClusterScience (2009)
50 nm
Porous silica (200 nm)Pores : 5 nm
550 m2/g
120 m2/g
Nanowires and Nanotubes Lateral dimension: 1 – 100 nm Nanowires & nanotubes exhibit novel physical, electronic and
optical properties due to – Two dimensional quantum confinement– Structural one dimensionality– High surface to volume ratio
Potential application in wide range of nanodevices & systems– Nanoscale sensors and actuators– Photovoltaic devices – solar cells– Transistors, diodes and LASERs Nanowire Solar Cell: The nanowires
create a surface that is able to absorb more sunlight than a flat surface
Anisotropic NanoMaterials
Synthetic nanomaterials utilized in biomedical applications Polymers, porous silicon, carbon nanotubes
Bone cell on porous silicon
Human cell on PSi
Porous silicon (PSi)
Formation and shape evolution of nano-heterostructures ( metal – carbon)
Chem. Mater., 2007, 19 (26), 6376-6378
Nanowire welding using DNA
T. MalloukPenn. State Univ.SH-DNA
Au
Complementary DNA strandson two wires
Quantum Dot Solar Cells
Complex functionalized Nanostructures
Carbon Nanotubes, (S. Iijima, 1991 )
Single nanotube ..transistor (1998, IBM) may replace silicon
Field effect transistors produced (Stanford/Cornell/Purdue)
Improved Carbon –based FET, IBM,2002 outperforms Si-based transistors,
twice current carrying capacity
World’s smallest computer logic circuit , IBM 2001
Sensors, Bio, NEMS
•
Electronics
• Challenges Challenges
• Control of diameter, chirality• Doping, contacts• Novel architectures (not CMOS based!)• Development of inexpensive Manufacturing processes
• Controlled growth• Functionalization with
probe molecules, robustness• Integration, signal processing• Fabrication techniques
Cost contributions from each process step (a–c) and fixed and variablecost contributions (d–f) for arc, CVD, and HiPco processes
Needs to be reduced
Needs to be reduced
Cost of synthesis
Cost of Labour
Ni-Titanate NanoTubes
as-prepared TNT Ni-TNT
300 C 400 C
500 C 600 C.
0 1 2 3 4 5
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
(c)
(b)
(e)
(f)
(g)
(d)
(h)
A/A
0
Irradiation time/hr
(a)
(a) Ni-TNT(b) 300 C (c) 400 C (d) 500 C (e) 600 C(f) 700 C (g) 800 C (h) 900 C
Photocatalytic degradation
Qamar et al Nanotechnology(2009)Beyond CNT
Biodegradable nanocomposite films for food packaging
Potato starch (PS), clay (C ) nanoparticles (Montmorillonite), bio-degradable polyester (PE) (Ecoflex SBX 7000)
Avella et.al, Food Chemistry, 93, 467(2005)
low overall migration limit and biodegradability
Nanostructured multiple emulsions in Food technology
Examples; oil-in-water-in-oil (O/W/O) and water-in-oil-in-water (W/O/W) emulsions
Water droplets
Oil droplets
Aqueous continuous phase
system for containing multiple food componentsto separate two reactive componentsto protect and release the component trapped within inner water droplets to a specific sites such as the mouth, stomach and small intestine
Thermal stability of primary, secondary and tertiary emulsions
Ze
ta p
ote
ntia
l
Biodegradable nanocapsules for the entrapment of drugsExample
Poly Lactic Acid (PLA) and Poly Ethyl Glycol (PEG) were used to prepare micellar like nanoparticles by precipitation/solvent evaporation method
Copolymer and the drug (procaine hydrochloride) were dissolved in acetonitrile and was precipitated in aqueous phase for the entrapment of drug into the assembly
T. Riley et al, 16, 147(1999)
(63.8 nm
PLA-PEG assembly can be successfully used as a host molecules for the
preservation of the drugs (as a guest molecules).
Core – shell nanostructures
Core
Shell
002200
Ag crystalline
TiO2
amorphous
5 nm
Methyl Orange
0 10 20 30 40 50 60 70 8070
75
80
85
90
95
100
% f
ree
met
hyl
ora
ng
e
Time (h)
Toxin Traps
Ganguli et al (2009)
SiO2
Metaloxide
Hollow shell
Hollow shells
ZnO @ CdS Core Shell Nanorods
Photocurrent
Assembly of core-shell on a substrate
CdS quantum dot sensitized solar cell based on a mesoporous TiO2 film : 1.24%J. Phys. Chem. C 2009,
IITD (2010)
Nanoelectronics
Smaller size of electronic components resistors, transistors, capacitors,
• Processors with increasing efficiency of computer by 106
• Higher transmission frequencies and more efficient utilization ofoptical spectrum to provide higher bandwidth
• Small mass storage devices: multi-tera bit levels
Dielectric Nanoparticles Dielectric Nanoparticles
Nanosized dielectric oxides (40-50 nm) will allow thin dielectric layers
Less dissipation factor
Need for miniaturization of device components
1990 limit (12 µm)
current feature size (chip) ~ 140 nm; by 2014 ~ 50-70 nm
MLCC ( Multilayer ceramic capacitor)For power line stabilization in the packaging of Si –based IC’s
( Pd /Ag)
+
Micron-sized Nanosized grainsHeat (Sinter)
Schematic Microstructure
Lower M. Pt.
Electroceramics : Nanocomposites
“( nµ) - Composites”
Barium titanium oxide
Enhancing the dielectric properties using nano-dopants
nμ-composite of BaTiO3
0
500
1000
1500
2000
0 5 10 15 20 25 30
wt% (Nano-BaTiO3)
0
0.02
0.04
0.06
0.08
0.1
D
D
At ~25oC
Sintered disk
Bulk BaTiO3 1 wt% BaTiO3
Dielectric constant is maximum at 1 wt
% composition
oscillatory nature
V. Shanker, T. Ahmad, H. Ip and A. K. Ganguli. J. Mater. Res., 21, 816 (2006)
Nanomaterials in Medical applications
Biosensor
DNA biosensor using impedance spectroscopy
• Rapid identification of DNA associated with bacterial contamination of food
• Immobilisation of DNA probes
• Hybridisation with sample DNA
• Impedimetric detection with interdigitated electrodes
D. Berdat, A.C. Martin-Rodriguez, F. Herrera, and M.A.M. Gijs, Lab on a Chip 8, 302-308 (2008); Daniel Berdat, L. Bernau, V. Sauvage, and M.A.M. Gijs, Proceed. Transducers’07 and Eurosensors XXI, Lyon, France, June 10-14, 2007, pp. 951-954.
Materials for applications in Gene therapy
viral vectors (toxic)Non – viral vectors…. Transfection ( Gene expression) is low
Drugs encapsulated in virus
Development of Calcium phosphate nanoparticles as a non-viral vector
Ca2+ complexes with DNA Enters cell Nucleus
Non – toxic
Technology transferred to American Pharmaceutical company
Anti – Cancer drug (Taxol)
No selectivity … toxic for cancer and normal cells
Polymeric micelle nanoparticles Encapsulate Taxol
Inject into body ( intravenous) The micelle develops perforations in the cancerous cells only Taxol is released Death of cancer cells
Technology transferred to Dabur, India
Prof A. N. Maitra, Delhi University
• More efficient catalytic converters
• Thermal barrier and wear resistant coatings
• Battery, fuel cell technology
• Improved displays
• Wear-resistant tires
• High temperature sensors for ‘under the hood’; novel sensors for “all-electric” vehicles
• High strength, light weight composites for increasing fuelefficiency
Scope of Nanomaterials for transportation
Carbon –based fibres, polymer-metal nanocomposites
• Improved collection, transmission, protection of information
• Very high sensitivity, low power sensors for detecting chem/bio/nuclear threats
• Light weight military platforms, without sacrificing functionality, safety and soldier security
- Reduce fuel needs and logistical requirements
• Reduce carry-on weight of soldier gear - Increased functionality per unit weight
•Miniature micro-machined silicon cantilever coated with sensitive polymer that detect vapors given off by explosives
Security
polymers
Detection of Explosives (RDX) in Seawater using Biosensors
Substrate
ImmobilizedRDX analog
Anti-RDXantibody
FreeRDX
Luminescent QD
Competition Assay
• QDs conjugated with anti-RDX antibodies
• Variation of PL of QD-bioconjugates bound to a surface prepared with RDX analogs
• Free RDX competes for bioconjugate and reduces PL signal
Materials of Major Interest Carbon nanotubes(CNT) ( electronics, sensors, high strength fibres)
Si Nanowires (biosensors)
Metal powders ( Al, B) ( space, defence)
BaTiO3 (electroceramics)
TiO2, GaN, ZnO, CdS (photovoltaics, energy)
Metal oxides (catalysts)
Fe2O3 , SiO2, Au ( biomedical applications)
Biodegradable polymers (Food & Drug industry)
Precise control of size and shape
Large scale synthesis
Self-assembly
GRAPHENErealized in 2004
(Novoselov, Science 306, 2004)
Predicted in 1947
Intrinsic graphene is a semi-metal or zero-gap semiconductor
remarkably high electron mobility at room temperature
pure graphene is transparent
ideal material for spintronicslight-emitting diodes (LEDs) , improved solar cells
Material of the Future
Large scale synthesis of pure Graphene : Challenge
Single molecule gas detection
Graphene nanoribbons
Graphene transistors
Integrated circuits
Transparent conducting electrodes
Reference material for characterizing electroconductive and transparent materials
Ultracapacitors
Graphene biodevices
Applications of Graphene
Compund % purity Avg size Quantity Cost (Rs)
BaTiO3 99+ 30-50 nm 25g 3638
CaTiO3 99.9 60-100 nm 25g 5395
CaZrO3 99.7 10-20 nm 25g 6540
CNT (single walled) 50 (Arc method) 1.2-1.5 nm * 2-5 μm 250 mg 5290
CNT (single walled) 50 (CVD) 1.1 nm * 0.5-100 μm 250 mg 13860
CNT (doublewalled) 50 (CVD) 1.3-2.0 nm * 50 μm 250 mg 13860
Mixture of Anatase and rutile 99.9 25-70 nm 25g 2620
Anatase 99.7 5 nm 50g 4982
Rutile 99.5 25g 2399
Silica 99.5 10 nm 50g 3696
Silica 99.5 15 nm 50g 3360
Cost of some nanomaterials
Molecules are important ( Molecular electronics)
30 nm
Bottom –up approach
The future : self assembled circuits with molecular components
Molecular machines
motor proteins
Synthetic molecular motors
Chemically driven rotary molecular motors
first example : Kelly and co-workers in 1999 rotation takes place in five steps
amine group present on the triptycene moiety is converted to an isocyanate group
Light-driven rotary molecular motors
Photochromic molecular switches
Prepared from Au-Ni nanorods (alumina membrane as the template )
The rotor is propelled by H2O2.
The angular velocity can be varied by H2O2 concentration and Ni segment length.
• rotational actuators• switches• valves• power sources
Fourier-Bidoz et.al., Chem. Commun. (2005) (4), 441
Nanodevices
Crossbar memory circuit (160 KB)
• Green , Heath et. al. Nature, 445, 414 (2007)
400 Ti n.wires covered by 400 Pt nanowires
By SNAP method400 Si nanowires
A Molecular switch tunnel junction (1 bit)
1011 per sq.cm
rotaxane molecules between the electrodes
33 nm pitch achieved
Size of One WBC13 microns
Predicted for 2020 by normal techniques
bistable [2]rotaxane used as
storage unit in the crossbar memory (molecular switch)
Green et. Al. Nature, (2007)
circumrotation
translation
Si nanowire
Pt/Ti nanowire
TTF TTF+
Balzani et al , J. Org Chem (2000)
Molecular shuttle
passive nano items developed : sunscreens, tennis rackets, stain/water-resistant clothing, and other high-tech products.
cars that automatically repair scratches wiper-less windshield cleaners
nanofoods such as fat-free donuts, cholesterol-lowering cheeseburgers, and “smart” grocery packaging materials that prevent food from spoiling.
2000-2005
2005-2010
products that change states during use
Development of Nanotechnology based products
To have transformable devices (easy to carry and use) leads the way from foldable, sliding, and bendable devices towards more wearable electronics.
In the near Future
protect the core electronics and achieve good reliability, i.e., “washable electronics”.
paper or fabric in ink infused with nanoparticles: lightweight paper batteries
stretchable, conductive textiles - capable of storing energy eTextiles
Nokia Morph ( joint venture between Nokia and Cambridge University )
Nanostructure-based smart device for sensing, communication, time, mobile, user friendly, self charging and self cleaning
• http://www.youtube.com/watch?v=IX-gTobCJHs
effective integration of electronics to device mechanicsoptimized design with multifunctional materials
challenges
With electricity : sizeable voltage is needed and the process is not very efficient
catalysts : a smaller voltage
Production of oxygen and hydrogen gas powered by solar photovoltaic cells
Mimic a green Leaf : A Photoelectrochemical cell can help to split water
Mostly with UV light
low conversion efficiencies and relatively high cost.
.
No material capable of catalyzing reaction with visible light and a QE larger than 10%
Store H2 , Couple with O2 in a Fuel CellEnergy ( in absence of Light)
Energy from water
• Cobalt-based Phosphate (Photocatalyst)
• 30kWh from one bottle of water (4h of sun)
• Daniel Nocera ( MIT) ARPA – Energy meeting, USA
March 2, 2010
How expensive is the catalyst ??? Turnover Number ???
H2O + CO2 H2 + O2 + carbohydrates catalyst
c
111
Rod shaped copper particles
20 nm
cube shaped copper particles
-0.001
-0.0005
0
0.0005
0.001
0 50 100 150 200
Cu-cube shapedCu-rod ShapedCu-Speherical Shaped
Time (sec)spherical shaped copper particles
Hydrogen evolution reaction
Ganguli et al 2010
Shape-dependent Copper nanostructures as electrocatalysts
proteins or viruses that build small batteries
nanostructures that create a lattice on which bone or other tissues can grow
“smart” dust strewn over an area that sense the presence of humans and communicates their location
devices that find and destroy cancer cells without harming neighboring tissues.
Nanotechnology: incredible products predicted for the future
2010-2015
Nanomaterials that self-assemble to achieve a final goal
Beyond 2030
humanity to transcend its biological limitations _interface directly with supercomputers and their stored intelligence
2015-2020
nanobots
computers will be able to sense and respond to human thoughts
render hazardous materials harmlessenrich farmlands by placing correct amounts of oxygen and nutrients into the soil, and roam through bodies analyzing vital conditions and displaying health
information directly on the skin (like a temporary tattoo). tissues and organs will be grown inside the body using stem cell and genetic
engineering techniques
2020 to 2030
tiny computerized nanobots that maintain perfect health in every cell
organic memory devices which would capture memories directly from our brain
Most complex molecules are synthesized atom by atom chemically
Self-organization leads to complex supramolecular entities
Brain -----Most Complex computer , made of molecules , run by molecules/ions
Life is possible because of chemical information processing
Influenced by some lectures of Jean Marie Pierre Lehn , N. L. in Chemistry, 1987
Some Thoughts
The Key is to use chemistry ( solution – based processes) together with the knowledge of biologically relevant molecules and processes
Ultimate Challenge
• Utilizing self-assembly and molecular recognition, different molecular scale “building blocks” may be combined together to tailor active, smart materials to mimic cells, organs and living beings
Department of Science & Technolgy, Govt. of IndiaNanomission, Physical Chemistry & ( IITD-EPFL) projectsMinistry of Human Res. & Dev., Govt. of India Council of Scientific & Industrial Research, Govt. of India