Maxim V' Kuznetsov

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Institute of Structural Macrokinetics and
Materials Science Russian Academy of Sciences
p/o Chernogolovka, Moscow region, 142432 Russia
SHS OF COMPLEX OXIDE MATERIALS STATE
AND PERSPECTIVES OF DEVELOPMENT
Maxim V. Kuznetsov Laboratory for Synthesis of
Functionalized Oxide Materials, 28-th November
2008
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Combustion synthesis of complex oxide materials

• M.V. Kuznetsov, ISMAN (Russia) et al.

The most effective scheme for SHS-synthesis
Niobates and tantalates of alkaline
and transition metals
Other ways of SHS complex oxides utilization
HTSC
Ferrites
Task Direct producing of compact materials and
articles from SHS. Tc increasing. Powder
technology installation.
Task Single crystals growth (example
- gadolinium molybdate)
Task Direct producing of compact materials and
articles from SHS

• Alternative power sources.
• Fuel Cells.
• Components of Li-ion batteries.
• SHS of functional oxides.
• Mineral ores and industrial
• wastes utilization for refractories
• producing.
• Radioactive wastes neutralization.

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Experimental setup for EMF registration
Potentiometer (V, t)
W electrode (-)
W electrode()
Quartz boat
Green mixture
U
T
c
Thermocouples

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Self-generated electric signals in the processes
of heterogeneous combustion of condensed systems
EMF of combustion
I type
II type
III type
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Dependence of the EMF of combustion vs time in
the SHS processes of iron-containing systems with
participation of solid oxidizers
Systems containing alkaline and alkaline-earth
peroxides
Systems containing alkaline and alkaline-earth
perchlorates
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Dependence of the EMF vs time in the SHS
processes of chromium-containing systems with
participation of solid oxidizers
The summarized maximal EMF in the studied
combustion processes may exceed 2V. It is because
of this chemical system containing potassium
compound, which is having one of the highest EMF
1020 mV in the whole Periodic system. The
maximal EMF of combustion for such system is
equal to the sum of EMFs from the different
streams produced by its compounds after oxidizers
decomposition and fuel oxidation K Cl7
Cr6 1020 mV 755 mV 337 mV (The whole sum
2.12 V).
Systems containing alkaline and alkaline-earth
peroxides
Digital experimental results of the temperature
distribution of multi thermocouple studies (a)
and its 3D-graph computer view (b) trough 30 mm
lengths cuvette during the combustion wave
front propagation in SHS-SLS process.
Digital experimental results of the temperature
distribution of multi thermocouple studies and
its 3D-graph computer view through 30 mm lengths
cuvette during the combustion wave front
propagation in SHS-SLS process
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SHS OF FERRITES STATE AND PERSPECTIVES OF
DEVELOPMENT
Prof. I. P. Parkin and Dr. M.V. Kuznetsov, UCL
(UK) - ISMAN (Russia)
1,2 Transient recorders 3 Permanent magnet 4
Thermally insulating shell 5
Chromel-Alumel thermocouple 6 Reference
electrode 7 Probe electrode 8 Quartz
boat containing reaction mixture 9
Jack
Green mixture
1.1 T
Oxygen
Quartz tube
Halbach cylinder permanent magnet
Set-up for oxygen flow rate experiments in a
1.1 T magnetic field
Experiment set-up for SHS reactions in a magnetic
field of 0.27 T
Living Frog flying inside of the magnet
Electromagnet with applied field up to 20T
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New experimental approaches in combustion
synthesis of ferrite materials
Dr. M.V. Kuznetsov, ISMAN (Russia)
Photographs of an SHS reaction in a 1.1 T applied
magnetic field. The magnetic field direction is
vertical and the hourglass shape adopted by the
mixture can be seen. Times shown are from the
time the reaction was ignited, t  0 s. The
reaction is of La2O3 Fe Fe2O3 NaClO4 . The
photographs were taken from video camera footage.
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MAGNETIC FIELD AS A FACTOR OF SHS-FERRITES
STRUCTURE AND PHYSICO-CHEMICAL PROPERTIES
REGULATION (FOR BARIUM HEXAFERRITE - BaFe12O19)

• (results of Dr. M.V. Kuznetsov, Prof. I. P.
  Parkin et.al.)

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Hysteresis loops for BaFe12O19, produced in 1
zero field 2 applied field 1.1?
1
2
Qurie points for BaFe12O19, produced in 1
zero field 2 applied field1.1?
Structure of BaFe12O19 - SHS product ?) zero
field b) applied field 2?
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Experimental setup for SHS of MnFe2O4 under
conditions of applied electric field up to 2.2
kV/m
Two-coordinate potentiometer
Copper plate (II)
Endim 622.1
Thermocouple
Copper plate (I)
High-voltage wires
Regulating high voltage source (voltage up to 11
?V)
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?????? ??????? MnFe2O4 ? ????????????? ???? ?220
??/?
-

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Thermal Imaging SetUp

• Mikron 9100 series
• 2 x 3 mm Frame
• Real Time Data Collection
• Range 800-3000 ºC
• 1.3 - 2.8ºC

Ni Pellet Frame
NdFeB Magnets
Thermal Imaging Beam
16 mm Pellet of Green Mix
Protective Metal Shield
Aluminium Casing
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ESRF and Daresbury Results

• Work carried out on Beamline ID-11 (l 0.2952Å)

Scans at 110-130 ms Data collected at 50 ms
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New experimental approaches in combustion
synthesis of ferrite materials
Dr. M.V. Kuznetsov, ISMAN (Russia)
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New experimental approaches in combustion
synthesis of ferrite materials
Dr. M.V. Kuznetsov, ISMAN (Russia)
Set of images (after each 10 images or 0,3 s)
produced during the registration of SHS
To Analyse
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Magnetic and Mössbauer parameters of spinel
lithium ferrite and lithium ferrites-chromites
SHS products
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Experimental setup for 3d articles producing by
using combined SHS-SLS technological
approaches(YAGNd3 (?VANT 60) laser)

• Parameters of KVANT-60 laser
• Energy 24 W
• Laser beam diameter 50-100 microns
• Scanning surface area 50?50
• or 100?100 ?? (1024?1024 pixels)

Balancing system
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Biocompatible implants on the base of titanium or
nickelide titanium (nitinol) as well as barium
hexaferrite 3d samples synthesised via SLS
Barium hexaferrite BaFe12O19
SLS of titanium in the nitrogen ambience (TiN).
3D Laser cladding of titanium on the
stomatological dowel
Plates for cranioplactics. (pure Ti).
SLS of NiTi 3D part molar tooth
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Biocompatible implants based on Ti and Ti
nickelide, synthesized by SHS and SHS-SLS and
its practical application
Titanium
Titanium nickelide
?
Axial projection
Rats shoulder-blade with implants
?
Under etheric anaesthesia the rats fall has been
cutted out with preliminary treatment of the
operation field. The shoulder-blade has been
isolated and titanium or titanium nickelide pores
implants has been placed inside in the holes
which was specially made by drill. All the rats
was alive after the operations and were placed in
the vivarium. In general 14 rats from the
experimental group and 7 rats from the control
group was operated.
Laboartory for Synthesis of Functionalized Oxide
Materials ISMAN P.N. Lebedev Physics Institute
/LPI/, Samara Branch, Russian Academy of Sciences
Samara State Medical University and University
College London (UK)
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Why Research an Improved Microstructure
forCr2-xTixO3

• Commercially used for detection of reducing gases
• Cr2-xTixO3 is single phase for 0.01 lt x lt 0.4
• yet magnitude of response largely unaffected by
  Ti
• Dopant increases resistance (to 103-106
  W) (unmasks gas response)
• Dopant changes conductance to p-type (resistance
  increase)
• 3. Allows more accurate derivation of response
  curves
• 4. Dopant (Ti) segregates to surface creating new
  surface sites
• 5. Different adsorption sites for gas
  water (low humidity effect)
• Exhibits stable baseline resistance

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Introduction to the Technology
The oxide is printed over a gold inter-digitated
electrode pattern on an alumina tile (2mm2) with
a Pt resistance thermometer on the reverse side
as heater for operable oxide temperature around
400C. (Picture courtesy City Technology)
Dual electrode pattern interrogates upper and
lower parts of CTO sensing material to provide
discrimination based on concentration gradient
through material.
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Typical EtOH gas response (400 ?C) for 1500 nm
CTO film (x 0.05)
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CONCLUSION

• The first controllable SHS experiments for
  complex oxide materials was carried out in ESRF
  (Grenoble, France) and Daresbury (UK). As a
  result a full set of the X-ray spectra for the
  whole combustion process was produced which
  enabled to determine the crystallographic phase
  evolution
• Constant magnetic field produced by permanent
  magnet (up to 1.1T) or by electromagnet (up to
  20T) as well as dc electric field up to 2.2
  kV/m
• can be used for modification of combustion
  parameters and physico-chemical properties of
  final products
• Very sensitive thermal imaging method was
  established for study of the combustion
  characteristics for the whole SHS-processes. This
  method of Thermal Imaging Technique (TIT) is
  based on the continuous registration of the whole
  combustion process by using a highly-sensitive
  IR-camera and software developed by MIKRON
  Instrument Co.(USA)
• - The combine process of controlled Selective
  Laser Sintering (SLS) - SHS for powdered SHS may
  be realised with the optimal parameters of a
  laser influence, under which the reaction carries
  under a control regime.