Ukrainian Research of Nanomaterials for Energy and ... · of Nanomaterials for Energy and...

Ukrainian Research Ukrainian Research of Nanomaterials for Energy and of Nanomaterials for Energy and

Environment Protection ApplicationsEnvironment Protection Applications

EU-Russia/Ukraine Workshop,

Madrid, Spain, April 21-23, 2010

DrDr. . ??ndreyndrey VV. . RagulyaRagulya

IPMS, +38IPMS, +38--044044--4247435 4247435 ragulyaragulya@@ipmsipms..kievkiev..uaua

2121--23 April 201023 April 2010

Materials Innovation as a Prime Mover of 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

State Program of Ukraine

“NANOTECHNOLOGIES AND NANOMATERIALS”

in 2010-2014

State Program of UkraineState Program of Ukraine

““NANOTECHNOLOGIES NANOTECHNOLOGIES AND NANOMATERIALSAND NANOMATERIALS””

in 2010in 2010--20142014

EU-Russia/Ukraine Workshop

DEVELOPMENT OF NATIONAL NANOINDUSTRYDEVELOPMENT OF NATIONAL NANOINDUSTRY

Grounding on fundamental researches, Grounding on fundamental researches, discoveries of novel phenomena, size effects in discoveries of novel phenomena, size effects in properties of matterproperties of matter, , creation of processes creation of processes suitable for synthesis, design, assemblingsuitable for synthesis, design, assembling on on nanoscale of complex nanoscale of complex nanostructuresnanostructures. Program . Program supports technology development aimed at supports technology development aimed at manufacturing of various manufacturing of various nanostructuresnanostructures, , nanodevisesnanodevises etc.etc.

The main goal of the programThe main goal of the program


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 existingmaterials 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 GRP 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 securityand environment protection.

National NANO Initiative

The main feature of the Strategic Plan for

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 responds to the

global priorities.

The National Program provides powerful international

collaboration in nanotechnologies.

?NN

?

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 …

Management

Physics,Diagnostics & Modeling

of nanostructures Magnetism, optics

Sensors and actuatorsScreens and displays

Data storage

Nanomaterials forBiology & Medicine

Biocompatible ceramics

Tissue engineering

Biosensors

Implants

Chemistry of Nanostructures

Catalysis, fuel cellssensors

Membranes

Hybrid materials

Batteries

Materials Science & Technologies of Nanomaterials

Structural materials

Multifunctional nanos

Coatings & Films Nanocomposites

Structure of ProgramStructure of Program

Funding

1. PHYSICS of NANOSTRUCTURES

2. ECHNOLOGIES OF SEMICONDUCTING NANOSTRUCTURES

3. DIAGNOSTICS OF NANOSYSTEMS

4. NANOMATERIALS

5. NANOBIOTECHNOLOGIES

9 main directions of R&D9 main directions of R&D

6. NANOCHEMISTRY

7. NANOELECRONICS AND NANOPHOTONICS

8. SAFETY OF NANOTECHNOLOGIES

9. DEVELOPMENT OF NATIONAL NANOINDUSTRY

Some results in basic research

National academy of sciences of UkraineNational academy of sciences of Ukraine

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 −π+=∇δ−β+−α0)(

.=∇+

??PP λm??

PPP =∇+.

)( λ In particlesIn films

BaTiO3120 nm

PbTiO330 nm

1 – Theory, 2 – Experiment,

Dr. M. Glinchuk, Kiev


1

2

3

4

Log

(σ),

arb.

uni

ts

Temperature, 104/T, K–1

–4

–2

–6

–8

–10 8 9 10 11 12 13

ionic conductivity of ZrO2(Y) Electronic conductivity of CeO2(Gd) : 10 nm (1); 30 (2); 300 (3); 5000 nm (4).

Temperature, 104/? , ? -1 Temperature, 104/? , ? -1

log(

σ),r

el.u

nits

log(

σ),r

el.u

nits

First proposed the physical mechanism and theory of size effect in ionic and electronic conductivity of nanoceramics:

Comparison of theory and experiment

The prognosis is important for SOFC development

10 nm

1200 nm

10 nm

5000 nm


HYDROGEN ADSORPTIONHYDROGEN ADSORPTION BY CARBON BY CARBON NANOMATERIALSNANOMATERIALS

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

((toto 9 wt.9 wt.%)! %)! Due capillary condensation of hydrogen in Due capillary condensation of hydrogen in the surface layersthe surface layers of onion particles with of onion particles with

increasedincreased d (002)d (002)

5 nm

0,42 nm

0,34 nm

Material Specific Surface Area Hydrogen , wt.%

m2/g 77 ?, 3 MP?

SWNT 180 1.23

MWNT 18 3.35

Activated:

?60 3100 3.54

Carbon 3000 5.4

Onions 700 12

?60

SWNT

Dr. A. Dr. A. MykhaylykMykhaylyk


New structural form of carbon (? int)New structural form of carbonNew structural form of carbon ((?? intint))Synthesis from charcoal by high-temperature shock wave compression at:

? = 30 GP?, ? > 2500 ?? int 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 ? int – cubic cell with strong sp2 bonds (? = 3)Lattice of ? int (Cohen model of ? -6) easily transforms to diamond lattice (? = 4)

? int forms together with diamond and has a lattice structure

Prognosis of properties: bulk modulus is expected to be ? int (390 GP?) close to the bulk modulus of diamond (440 GP?)

Clusters

Dr. A. Kurdyumov, Kiev

17

The synthesis of refractory compound The synthesis of refractory compound nanofibersnanofibers and and composites on the base of them composites on the base of them

Si3N4

50 nm

TiN

Si3N4

Single crystal SiC- nanorods

Polycrystalline SiCnanowire

Single crystalTiB2- nanorods TiN, SiC, Si3N4, TiB2

and other compounds

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

(?extrusion: 350 °?, factor of elongation: 5)

Structure of quenched and

crystallized ribbon Al-Ni-Ce-Fe,Annealing at temperatures higher than 350°C

200 nm

Prof. Prof. MilmanMilman

Alloys of the systemAlloys of the system AlAl--FeFe--CrCr--TiTiresresppond to the requirements of ond to the requirements of

todaytoday’’s aviation industrys aviation industry

σ? > 14501450 ? P? at 300 °? ; δ > 5 % at room temperature


0 1 2 3 4 50

2

4

6

8

10

12

14IIIIII

εe s

, %

HIT

, ÃÏ à THE MAP OF STRUCTURE STATE TYPES

Nano-crystalline

Fine-Crystalline

Amorphous

NEW METHODOLOGY OF PROCESSING AND ANALYSIS OF THE RESULTS OF MATERIAL AUTHOMATIC INDENTATION

Fundamental indentation equation :

? IT / ?*= K⋅ (hs / hc) or ? IT / ?*= K⋅ (εes / ε?)

Calibration dependence and the map of structure state allows us to determine the type of structure state for material and also to control the testing reasonableness.

Macrocrystalline

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

-0,5 0,0 0,5 1,0 1,5 2,0

-1

0

1

2 ordered stage

disordered stage

lg(-

ln(I

))

lg(t)

1at.%

4at.%

10at.%

αβtg α = 0,93

tg β = 0,52

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


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

1001001010--3030AlAl22OO33, SiO, SiO22, TiO, TiO2 2 ((Labor.Labor., , PilotPilot))

Gas Flame SynthesisGas Flame Synthesis

20002000--30003000

4040--180180Cu, Fe, Mo, Ni, Co, W, WCCu, Fe, Mo, Ni, Co, W, WC--Co (Co (LabLab))

Reduction of oxidesReduction of oxides or or complex saltscomplex salts

26002600250250175175

12001200450450--15001500

55--2525

1515--5050

1100--2525

~20~20

1010--5050

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

((NdNd--YY--Al)Al)--O O garnetgarnet ((LabLab..), ), BaTiOBaTiO33, SrTiO, SrTiO33, (, (PilotPilot))

FeFe--CoCo--O, LaSrMnOO, LaSrMnO33, (, (LabLab..))

SiCSiC, BN, TiB, BN, TiB2 2 ((Lab, PilotLab, Pilot))

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

130130140140180180150150

88--202066--1515

2020--3030

AlAl22OO33, TiO, TiO22 ((PilotPilot))ZrOZrO22--n%Yn%Y22OO33, (, (PilotPilot) ) CeOCeO22, BaTiO, BaTiO3 3 ((LabLab))

HydroxyapatiteHydroxyapatite ((PilotPilot))

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

PricePrice, , USDUSD//kilokilo

Particlesize, nm

ObjectsMethod of synthesis

Physical methods developed & applied

11--88SiCSiC,, NbNNbN, TiN, , TiN, BB44CCMagnetron sputteringMagnetron sputtering

5050--9090160160--200200

4040--1801802020--5050

Cu, SiOCu, SiO22, B, B44C C ((pilotpilot))WC, Co, Ti (WC, Co, Ti (PilotPilot))

GrindingGrindingJetJet--attritionattritionCryogenic millingCryogenic milling

55--1515

2020--4040

C, Pt,C, Pt, AlAl22OO33, , SiCSiC, Si, Si33NN44, , ZrOZrO22, BaTiO, BaTiO33, TiB, TiB22 (LabLab..))Metals and alloysMetals and alloys ((PilotPilot))

Laser evaporation and Laser evaporation and synthesissynthesisElectric explosion of Electric explosion of conductorsconductors

30003000--50005000

15001500--20002000

55--3030Al, Ag, Au, Cu, Ni, Pd, Zn, Al, Ag, Au, Cu, Ni, Pd, Zn, C C includingincluding fullerenfulleren andandnanotubesnanotubes ((LabLab., ., PilotPilot..))AlAl22OO33, TiO, TiO22, ZrO, ZrO22 ((LabLab..))

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

PricePrice, , USDUSD//kilokilo

Particlesize, nm

ObjectMethod of synthesis

Combined synthesisCombined synthesisSynthesis combines colloidal processes, microwave treatment

and powerful ultrasonication to get monosize nanoparticles

Particle size of 6 to 12 nm Particle size of 20 to 40 nmPilot production developed of both products for SOFC techn.Dr. T. Konstantinova et al.


10Sc1CeSZ powders: 10Sc1CeSZ powders: sizes & surfacesizes & surface

2020--505048.2848.28UkrUkr milledmilled

2020--50506.206.20UkrUkr asas--preparedprepared

Particle Particle size, size,

nmnm 2,32,3))

Specific Specific surface, surface, mm22/g/g 11))

PowderPowder

1) BET; 2) TEM; 3) Laser granulometry

Total conductivity of Total conductivity of 10Sc1CeSZ electrolytes10Sc1CeSZ electrolytes

Grain size 90 nm

Total conductivity of Total conductivity of 10Sc1CeSZ electrolytes 10Sc1CeSZ electrolytes vs. oxygen partial pressurevs. oxygen partial pressure

bioimplants

Scalpels

Solid –oxide electrolytes

Parts for generating units

Tubular and plate-like

Parts for medical applications

Concentrating nanocrystalls Pt and Pd on templates from mesoporous 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/Pdheteronanoparticles , SiO2

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

a b

20 ?? 20 ??

20 ?? 20 ??

Dr. A. Tolmachev,

45-6050-70

1,0-1,2

120< 240

Wall open porosity, %Pore size, nmCTE (20-800 ?? ), ?? ×10-6

Operating temperature, ??Cold start , ??Continuous (100% conv.)

Cold start ceramic soot filters and catalytic converterspotential segment of market ~ $1B

20 ??

Functional nanoparticles and surfaceFunctional nanoparticles and surface--active active oligoelectrolytesoligoelectrolytes with genuine biocide activity.with genuine biocide activity.

Silver nanoparticles in the tooth channels

Dr. A. Zaichenko, Lviv

Potential Segment of Market - $20 B in 2015


ApplicationApplication of of ««NanoluminoforesNanoluminofores»» for identification, for identification, diagnostics anddiagnostics and monitoring of biomonitoring of bio--objectsobjects

Dr. Yu. Malyukin, Kharkov

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

durable storage; • Cell therapy;

Depolarized fibroblastmitochondria

Activated fibroblast mitochondria

Organic luminescent nanotubeslocalized on membranes of

mitochondria

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.

Bio-nanocomposite demonstrates accelerated growing through the implant of natural bone due to the mechanism of dissolution-re-precipitation

Implant samples

BioBio--compositecomposite

bonebone

Growing through

start

finish

Implant from “Synthebone” biocomposite

Segment of market will reach $15-20 B in 2020

SPS+SHS of TiN-TiB2 in-situ nanocompositeSPS+SHS ofSPS+SHS of TiNTiN--TiBTiB2 2 inin--situsitu nanocompositenanocomposite

0 40 80 120 160 2000

20

40

60

80

3

2

1

T,0 C

∆l/l,

%

τ, c0

500

1000

1500

Densification kinetics

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

Structure (SEM)

TiH2

BN

10.53260TiB2/40TiN

8.08.019193636TiBTiB22/64TiN/64TiN

KKICIC, , ? ? ?? ? ? ?? 1/21/2HV, HV, ?? ??? ?????????????

Prospective cutting tool ceramics

Unique SiC-C nanopowders and Superhard ceramics based on them

TEMHR of nanoparticles SiC-Cof 10 to 70 nm

High hardness SiC-C to 42 GP?

Hardness vs. microdeformationsDr. ? .Gadzira, Kiev


Nanostructured multilayer capacitorsNanostructured multilayer capacitors

0

1

2

3

4

5

6

1998 2000 2002 2004 2006 2008 2010 2012 2014Time (years)

Die

lect

ric

Th

ickn

ess

(um

)

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 µµmm in 2007 in 2007 0.2 0.2 µµmm in 2011in 2011 100 nm in 2013100 nm in 2013

Now we have

Revolutionary !

µm ceramics

Now we haveNow we have::

•• Pilot version of production for Pilot version of production for nanopowdernanopowder sized of sized of 1010--1515 nmnm

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

SuperSuper--capacitors with nanostructured capacitors with nanostructured carbon electrodescarbon electrodes

0 5 10 15 20 250,0

0,2

0,4

0,6

0,8

1,0

Vol

tage

, V

t, minutes

High specific energy and power, lack of side reactions and Faraday processesare good pre-requisites for super-capacitors based on carbon materials originating from bio-raw-materials. Best specific capacity at the level of

200 F/g remains stable for 106 cycles of charge/discharge.

100 101 102 103

0,90

0,92

0,94

0,96

0,98

1,00

? dis

./???

?.

Number of cycles

Developed a technology of carbon-based materials, to make thin layer packaging of electrodes in super-capacitors.

Discharge of super-capacitor ? ????-0,25using different resistors (O)

10-2 10-1 100 101 102 103 104 1050.0

0.2

0.4

0.6

0.8

1.0

?????-0,25

100

101.00.01 0.1

U, V

Time, h

ParametersType of SCap Capacity,

FSpecific

capacitance, ? -hours

Internal resistance,

O

Discharge current,

?

Weight

kg ? ? ? ? ?-0,25 1000 0,25 0,005 100 0,440

? ? ? ? ?-1,25 5000 1,25 0,001 500 2,050

Super-capacitor

Technologies available for pilot stage in Ukraine from

Ukrainian raw materials:

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.

•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.

Raw materialRaw materialApplicationApplication

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.

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 to R&D process with term of practical realization for 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 YOUTHANK YOUTHANK YOU

IPMSKiev, Ukraine

IPMS mission is the Ukrainian national leadership in the fundamentals of modern materials science advanced scientific and engineering services, technical consulting, and contract research and development in the field of materials science and advanced technology of metal, ceramic and composite materials.

Frantsevich Institute for Problems in Materials ScienceNational Academy of Science of Ukraine

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