General Overview General Overview on Nanotechnologies State of on Nanotechnologies State of

Play in UkrainePlay in Ukraine

Thematic International Conference on Bio-, Nano-, and Space Technologies, Ljubljana, Slovenia, March 10-12, 2008

DrDr. А. Аndrey Vndrey V. . RagulyaRagulya

IPMS, +38-044-4247435 IPMS, +38-044-4247435 ragulya@ipms.kiev.uaragulya@ipms.kiev.ua

12 March 20012 March 20088

Materials Innovation as a Prime Mover Materials Innovation as a Prime Mover of Economic Developmentof Economic Development

Materials Innovation as a Prime Mover Materials Innovation as a Prime Mover of Economic Developmentof Economic Development

Complication of structure, engineering, atom-scale assembling

increasing number of functions per volume unit

О N

NА

Complicated multifunctional

systems, nanocomposites. Self-organization

in inorganic systems

Miniaturization of

devises

Systems which act in «NANO»-

scale only, supramolecular-and biosystems

Size effect in properties of nanosystems

The smaller is the scale,

the more scaled the problems are …

““NANOSYSTEMSNANOSYSTEMS, , NANOMATERIALS AND NANOMATERIALS AND NANOTECHNOLOGIES”NANOTECHNOLOGIES”

the Program of the the Program of the National Academy of Sciences of UkraineNational Academy of Sciences of Ukraine

Chairman of academic board – A.P. Shpak

““NANOSYSTEMSNANOSYSTEMS, , NANOMATERIALS AND NANOMATERIALS AND NANOTECHNOLOGIES”NANOTECHNOLOGIES”

the Program of the the Program of the National Academy of Sciences of UkraineNational Academy of Sciences of Ukraine

Chairman of academic board – A.P. Shpak

Maintain fundamental researches, which Maintain fundamental researches, which result in discovery of novel phenomena, result in discovery of novel phenomena, properties of materialsproperties of materials, , creation of creation of processes suitable for synthesis, design, processes suitable for synthesis, design, assemblingassembling on nanoscaleon nanoscale, , modeling and modeling and simulation of complex nanostructures and simulation of complex nanostructures and study of study of their behavior. Program supports their behavior. Program supports technology development aimed at technology development aimed at manufacturing of various nanostructures.manufacturing of various nanostructures.

The main goal of the The main goal of the programprogram

Management

Physics,

Diagnostics & Modeling of nanostructures Magnetism, optics

Sensors and actuatorsScreens and displays

Data storage

Nanomaterials for

Biology & Medicine

Biocompatible ceramics

Tissue engineering

Biosensors

Implants

Chemistry of Nanostructures

Catalysis, fuel cells sensors

Membranes

Hybrid materials

Batteries

Materials Science & Technologies of Nanomaterials

Structured materials

Multifunctional nanos

Coatings & Films Nanocomposites

Structure of ProgramStructure of Program

Funding

1. NANOPHYSICS AND NANOELECTRONICS

2. DIAGNOSTICS OF NANOSYSTEMS

3. ELECTRONIC AND ATOMIC STRUCTURE OF NANOMATTER

4. MODELING OF NANOs

5. BIO-INERT NANOSYSTEMS

6. BIO-ACTIVE NANOSYSTEMS

National academy of sciences of UkraineNational academy of sciences of Ukraine

4 blocks include 12 main directions of research4 blocks include 12 main directions of research

7.  SUPRAMOLECULAR CHEMISTRY

8. SURFACE CHEMISTRY OF NANOSTRUCTURES

9.  COLLOIDAL NANODIMENSIONAL SYSTEMS

10.  TECHNOLOGY OF MULTIFUNCTIONAL NANOMATERIALS

11. NANOSTRUCTURED FILMS AND COATINGS

12. BEAM TECHNOLOGIES

National academy of sciences of UkraineNational academy of sciences of Ukraine

Total number of institutions involved: 24 in ~60 projects

The multidisciplinary community unites physicists, chemists, biologists, materials scientists, medical

scientists and some others, around 1000 researchers.

Total annual funding: 12 M UAH (~1.6 M Euro)

Total funding of international projects in Nanos gives also around 1.5 M Euro.

NASU has bought expensive equipment for nano researches: Bruker NMR, HRTEM JEOL, HRSEM, AFM+STM JEOL, Nanoindenter etc.

National academy of sciences of UkraineNational academy of sciences of Ukraine

Some results in basic research

Nanostructured ferroelectricsNanostructured ferroelectrics ( (theorytheory))

PZT film on MgO substrate

The Eiler-Lagrange solution for non-uniform polarization P(r) has been achieved

)(4)( 232 PPEPPPTT c 0)(

.

грPP mгр

PPP .

)( In particlesIn films

BaTiO3 120 nm

PbTiO3 30 nm

1 – Theory, 2 – Experiment,

““NANOSYSTEMS, NANOMATERIALS and NANOTECHNOLOGIES”NANOSYSTEMS, NANOMATERIALS and NANOTECHNOLOGIES”

Dr. M. Glinchuk, Kiev

HYDROGEN ADSORPTIONHYDROGEN ADSORPTION BY CARBON BY CARBON NANOMATERIALSNANOMATERIALS

Carbon onionsCarbon onions demonstrate highest demonstrate highest physical adsorption capacityphysical adsorption capacity

((toto 1212 wt. wt.%)! %)! Due capillary condensation of Due capillary condensation of

hydrogen in the surface layershydrogen in the surface layers of of onion particles with increasedonion particles with increased d d

(002)(002)

5 nm

0,42 nm

0,34 nm

Material Specific Surface Area Hydrogen , wt.%

m2/g 77 К, 3 MPа

SWNT 180 1.23

MWNT 18 3.35

Activated:

С60 3100 3.54

Carbon 3000 5.4

Onions 700 12

С60

SWNT

Dr. A. MykhaylykDr. A. Mykhaylyk

““NANOSYSTEMS, NANOMATERIALS and NANOTECHNOLOGIES”NANOSYSTEMS, NANOMATERIALS and NANOTECHNOLOGIES”

New structural form of carbonNew structural form of carbon (С (Сintint)) New structural form of carbonNew structural form of carbon (С (Сintint))

Synthesis from charcoal by high-temperature shock wave compression at: Р = 30 GPа, Т 2500 К

Сint shows density of 2,9 g/cm3 – intermediate between one of graphite (2,2 g/cm3) and diamond (3,5

g/cm3)The basis of lattice of Сint – cubic cell with strong sp2 bonds (к = 3)

Lattice of Сint (Cohen model of Н-6) easily transforms to diamond lattice (к = 4)

Сint forms together with diamond and has a lattice structure

Prognosis of properties: bulk modulus is expected to be Сint (390 GPа) close to

the bulk modulus of diamond (440 GPа)

Clusters

Dr. A. Kurdyumov, Kiev

Extrusion-consolidation of amorphous powders of Al-Ni-Ce-Fe into bulk pieces

(Тextrusion: 350 °С, factor of elongation: 5)

Structure of quenched and

crystallized ribbon Al-Ni-Ce-Fe,

Annealing at temperatures higher

than 350°C 200 nm

““NANOSYSTEMS, NANOMATERIALS and NANOTECHNOLOGIES”NANOSYSTEMS, NANOMATERIALS and NANOTECHNOLOGIES”

Dr. SlipenyukDr. Slipenyuk

Alloys of the systemAlloys of the system Al-Fe-Cr-TiAl-Fe-Cr-Ti resresppond to the ond to the requirements of today’s aviation industryrequirements of today’s aviation industry   

в > 14501450 МPа at 300 С; > 5 % at room temperature 

Segregation and ordering of Pr3+ ions on a surface of nanoparticles Y2SiO5:Pr3+ due to ion radius difference

RPr3+ = 1.16 Å, RY3+ = 1.06 Å 

Shell – area of small distances between Pr ions. Ordered state

Shell – area of small distances between Pr ions. Ordered state

Core- area of large distances between Pr3+ ions. (Disordered state)

Core- area of large distances between Pr3+ ions. (Disordered state)

Institute for Scintillation Materials, NAS of UkraineYu.V. Malyukin, Phys.Stat.Sol.(b), 244(9) (2007)

NanotechnologiesNanotechnologies

for commercialization for commercialization

right now!right now!

Synthesis of nanoparticlesSynthesis of nanoparticlesSynthesis of nanoparticlesSynthesis of nanoparticlesChemical technologies developed & applied in Ukraine

Method of synthesis Objects Particle size, nm

PricePrice, , USDUSD//kilokilo

Wet chemical synthesisWet chemical synthesis co-co-precipitationprecipitation, , hydrolysis hydrolysis hydrothermal, hydrothermal, emulsionemulsion

AlAl22OO33, TiO, TiO

22 ( (PilotPilot))

ZrOZrO22-n%Y-n%Y22OO33, (, (PilotPilot) )

CeOCeO22, BaTiO, BaTiO

3 3 ((LabLab))

HydroxyapatiteHydroxyapatite ( (PilotPilot))

88-20-20

6-156-15

20-3020-30

130130

140140

180180

150150

Thermal decomposition of Thermal decomposition of unstable precursorsunstable precursors, , Spray Spray pyrolysispyrolysis

Au, Ag, Cu, Fe, Ni, (Au, Ag, Cu, Fe, Ni, (LabLab..) )

(Nd-Y-Al)-O (Nd-Y-Al)-O garnetgarnet ( (LabLab..), ),

BaTiOBaTiO33, SrTiO, SrTiO

33, (, (PilotPilot))

Fe-Co-O, LaSrMnOFe-Co-O, LaSrMnO33, (, (LabLab..))

SiC, BN, TiBSiC, BN, TiB2 2 ((Lab, PilotLab, Pilot))

5-255-25

15-5015-50

110-0-2525

~20~20

10-10-5050

26002600

250250

175175

12001200

450-1500450-1500

Reduction of oxidesReduction of oxides or or complex saltscomplex salts

Cu, Fe, Mo, Ni, Co, W, WC-Cu, Fe, Mo, Ni, Co, W, WC-Co (Co (LabLab))

40-18040-180 2000-2000-30003000

Gas Flame SynthesisGas Flame Synthesis AlAl22OO33, SiO, SiO

22, TiO, TiO2 2 ((Labor.Labor., ,

PilotPilot))

10-3010-30 100100

Physical methods developed & applied

Method of synthesis Object Particle size, nm

PricePrice, , USDUSD//kilokilo

Evaporation – condensation Evaporation – condensation in the inert gas or vacuumin the inert gas or vacuum

Al, Ag, Au, Cu, Ni, Pd, Zn, Al, Ag, Au, Cu, Ni, Pd, Zn,

C C includingincluding fullerenfulleren andand nanotubesnanotubes ( (LabLab., ., PilotPilot..))

AlAl22OO33, TiO, TiO

22, ZrO, ZrO22 (Lab(Lab..))

5-305-30 3000-3000-50005000

1500-1500-20002000

Laser evaporation and Laser evaporation and synthesissynthesis Electric explosion of Electric explosion of conductorsconductors

C, Pt,C, Pt, AlAl22OO33, SiC, Si, SiC, Si

33NN44, ,

ZrOZrO22, BaTiO, BaTiO

33, TiB, TiB22 (LabLab..))

Metals and alloysMetals and alloys ( (PilotPilot))

5-155-15

20-4020-40

GrindingGrinding

JetJet--attritionattrition

Cryogenic millingCryogenic milling

Cu, SiOCu, SiO22, B, B44C C (pilot)(pilot)

WC, Co, Ti (Pilot)WC, Co, Ti (Pilot)

40-18040-180

20-5020-50

50-9050-90

160-200160-200

Magnetron sputteringMagnetron sputtering SiC,SiC, NbN, TiN, NbN, TiN, BB44CC 11--88

Combined synthesisCombined synthesisSynthesis combines colloidal processes, microwave treatment

and powerful ultrasonication to get unisize nanoparticles

Particle size of 6 to 12 nm Particle size of 20 to 40 nm

Pilot production developed of both products for SOFC techn.

Dr. T. Konstantinova et al.

Concentrating nanocrystalls Pt and Pd on templates from silicon dioxide nanoparticles

TEM images of SiO2/Pt heteronanoparticles , SiO2

diameter 40 nm, Pt shell: (a) - individual nanocrystals 3 nm,(b) - full covering thickness 7 nm

a b

TEM images of SiO2/Pd heteronanoparticles , SiO2

diameter 40 nm, Pd shell: (a) - individual nanocrystals 5 nm,(b) - full covering thickness 7 nm

a b

20 нм 20 нм

20 нм 20 нм

Dr. A. Tolmachev, Kharkov

Functional nanoparticles and surface-Functional nanoparticles and surface-active oligoelectrolytes with genuine active oligoelectrolytes with genuine

biocide activity.biocide activity.

Silver nanoparticles in the tooth channels

Dr. A. Zaichenko, Lviv

Potential Segment of Market - $20 B in 2015

ApplicationApplication of «Nanoluminofores»of «Nanoluminofores» for identification, for identification, diagnostics anddiagnostics and monitoring of bio-objectsmonitoring of bio-objects

Dr. Yu. Malyukin, Kharkov

Fields of application:• Medical diagnostics;• Biological research;• Control of bio-processes in the course of

durable storage; • Cell therapy;

Depolarized fibroblast mitochondria

Activated fibroblast mitohondria

Organic luminescent nanotubes localized on membranes of

mitohondria

Cryo-TEM image of organic luminescent nanotubes

Global market of biomarkers is around $6 B, next 5 years it will growth to $12.8 B.

ImplantImplant based onbased on bio-compositebio-composite “Syntekost”“Syntekost”

In this sort of biocompositeIn this sort of biocomposite with with

improvedimproved resorbtion,resorbtion, the bone tissuethe bone tissue

((dark browndark brown) ) growthsgrowths uniformlyuniformly

throughout the synthetic bone throughout the synthetic bone ( (light light

brown collorbrown collor).).

Dr. V. Dubok Segment of market will reach $200 B in 2020

SPS+SHS ofSPS+SHS of TiN-TiBTiN-TiB2 2 in-situin-situ nanocompositenanocompositeSPS+SHS ofSPS+SHS of TiN-TiBTiN-TiB2 2 in-situin-situ nanocompositenanocomposite

Densification kinetics

Substantially nonisothermal Substantially nonisothermal process, heating rates >600 C/minprocess, heating rates >600 C/min

Structure (SEM)

TiH2

BN

СоставСостав HV, HV, ГПаГПа KKICIC, , МПа мМПа м1/21/2

3636TiBTiB22/64TiN/64TiN 1919 8.08.0

60TiB2/40TiN 32 10.5

Prospective cutting tool ceramics

Unique SiC-C nanopowders and Superhard ceramics based on them

TEMHR of nanoparticles SiC-C of 10 to 70 nm

High hardness SiC-C to 42 GPа

Hardness vs. microdeformationsDr. М.Gadzira, Kiev

Nanoscale multilayer capacitorsNanoscale multilayer capacitors

0

1

2

3

4

5

6

1998 2000 2002 2004 2006 2008 2010 2012 2014

Time (years)

Die

lec

tric

Th

ick

ne

ss

(u

m)

Historical

Projected

~0.2um

~0.5umin 2007

~0.1um

Targeting at $1.5 B market we will be at: Targeting at $1.5 B market we will be at:

0.5 0.5 μμm in 2007 m in 2007 0.2 0.2 μμm in 2011m in 2011 100 nm in 2013100 nm in 2013

Now we have

Revolutionary !

0.9m

NiNi

ceramics

Now we haveNow we have::

• Pilot version of production for Pilot version of production for nanopowdernanopowder sized of sized of 1010-15-15 nmnm

• Technology of denseTechnology of dense 98 %98 % ceramicsceramics with with grain size ofgrain size of 4455 nm nm

Global market of nanomaterials is intensively growing (AAGR > 10%)

and will achieve $150 Billion in 2010.

Ukraine is able to contribute to this segment of economy and develop new products using Ukrainian IP

and raw-materials

Summary

Developed and patented Ukrainian technologies for Developed and patented Ukrainian technologies for synthesis synthesis of of nanosize particulate systems:nanosize particulate systems: some of some of them are on a stage of pilot productionthem are on a stage of pilot production. . Novel Novel products need investments to be transferred from products need investments to be transferred from laboratories into industry.laboratories into industry.

Technologies available for pilot stage in Ukraine from

Ukrainian raw materials:

ApplicationApplication Raw materialRaw material

•Solid oxide fuel cells

•Multilayer ceramic capacitors

•Ceramic Implants

•Hard and wear resistive nanoceramics

•Ionic batteries

•Ceramic thermal barrier coatings

•Photocatalysts

•Ceramic catalytic converters for

automobiles.

deposit of zirconium, manganese, and rear earths

deposit of titanium ores

no problem with phosphates

titanium, zirconium…

huge deposit of graphite of

high quality

zirconium and rear earths

titania,

Silica, alumina etc.

Taking into account substantial effect of nanotechnologies on traditional materials science discipline, DELPHY analysis has recommended the following formulation of strategic priority of science and technology development in Ukraine:

Nanoscience, nanotechnology, novel materials and technologies for their production and treatment  

From this priority, the mid-term and long-term state interest were formulated as follows:

- novel materials of structural and functional destination, technologies of their manufacturing and treatment, including technologies improving the reliability and endurance of existing materials owing to analysis, design and operation on nanoscale;

- nanomaterials and nanotechnologies for energy production, transformation, storage and saving, including new hydrogen technologies (production, storage and usage of hydrogen fuel);

- nanodevices, nanomaterials and nanotechnologies for biomedical applications health care, diagnostics and decease prevention;

- materials and technologies for environment protection and utilization of wastes;

- materials and nanodevices for novel communication and information systems.

Targets:

- creation of new industry in Ukraine, environment friendly, automated, secure, capable to substitute in part the conventional production and old «dirty» industry,

- substantial increase of AAGR due to enlargement of “high tech” sector of economy and creation of high quality jobs.

- improvement of state security

- substantial improvement of life quality and enlargement of average life owing to development and commercialization of nanotechnologies in biomedicine, agriculture, people security and environment protection.

National NANOProgram?

The main feature of Strategic Plan of

nanotechnologies in Ukraine is to be it’s openness

with respect to the world – Ukraine cannot develop

nanotechnologies remaining isolated from the rest of

the world and global market, thus, the priorities of the

National nanotechnology program must respond to

the global priorities.

The National Program has to provide powerful

international collaboration in nanotechnologies, for

instance to meet priorities of EU FP7.

Measures:

To fund the State multidisciplinary program «Nanosciences and Nanotechnologies in Ukraine» in amount of at least 750-770 M UAH per year for next 5 years.

Establish laboratories equipped by modern research and technological units, organize clean rooms of high standard and certification center.

Organize 4 nanotechnology research & education centers for masters and graduate students in Kiev, Lvov, Kharkov and Donetsk, each funded in amount of 20 M UAH/year.

Up to 25% of funds (to $30 MEuro) provide for collaboration with EU through 7 Framework Program using instruments of international expertise.

Opportunities:

Participation of Ukrainian NANOscientists in 7FP will be helpful for:

•promotion Ukrainian businesses to invest more risky projects, creation and investment start-up companies, contributing more to R&D process with term of practical realization up to 5-6 years

•certification of NANO products

•encouraging young generation in NANOtechnology development for the sake of competitiveness of Ukrainian economy and higher quality of people life in Ukraine.

Thank you for attention !