CARBON NANOMATERIALS CARBON NANOMATERIALS SYNTHESES UNDER SYNTHESES UNDER
NONEQUILIBRIUM CONDITIONSNONEQUILIBRIUM CONDITIONS
SERGUEI ZHDANOKSERGUEI ZHDANOKNATIONAL ACADEMY OF SCIENCES OF NATIONAL ACADEMY OF SCIENCES OF
BELARUSBELARUS
CARBON NANOTUBES CARBON NANOTUBES FABRICATION IN FABRICATION IN
DISPROPORTINATION DISPROPORTINATION REACTIONREACTION
CO + CO CO2 + CEa = 5.5 eV
Reactants А + В С + D Products
v
a
a
kT
E
E eN
Энергетический выигрыш
3Vр
нер
СС
W
W
External action: electron impact (gas discharge) radiation (laser chemistry)
Ea
òåï ë î òà ðåàêöèè
ýí åðãèÿ àêòèâàö èè
âí
åøíå
åâî
çäåé
ñòâè
å Activation energy
Caloric effect
exte
rnal
actio
n
Nanomaterials Syntheses in Nonequilibrium Systems
Energy Saving
VIBRATIONAL NONEQUILIBRIUM IN CO UNDER VIBRATIONAL NONEQUILIBRIUM IN CO UNDER APHVD CONDITIONSAPHVD CONDITIONS
CO(v)
CO(w)
CO(v + 1)
CO(w-1)
CO(v) + CO(w) CO(v+1) + CO(w-1)
Ev = E1v[1- E/E1 (v-1)]
V-V PUMPING IN CO UNDER NONEQUILIBRIUM V-V PUMPING IN CO UNDER NONEQUILIBRIUM CONDITIONSCONDITIONS
w-1
w
v + 1v
wwvv
wwvv Q
kT
EQ ,1
,11,
1, exp
NONEBOLTZMANN VIBRATIONAL NONEBOLTZMANN VIBRATIONAL DISTRIBUTION IN CO UNDER NONEQUILIBRIUM DISTRIBUTION IN CO UNDER NONEQUILIBRIUM
CONDITIONSCONDITIONS
CO(v*) + CO(v*) CO2 + CEv* + Ev* 5.5 eV
1 1 0E /N , 1 0 -1 6 V cm 2
0
1 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
Ele
ctro
n en
ergy
bal
ance
, %
E la stic h ea tin g A tta ch m en tV ib ra tio n s N 2 E lec tro n ic N 2V ib ra tio n s C O E lec tro n ic C OV ib ra tio n s H 2 E lec tro n ic H 2D isso c ia tio n Io n isa tio n
V ib .C O
V ib .H 2
V ib .N 2
E lec .C O
E lec .N 2
D isso c .
Ion iz .E lec .H 2
E la stic
M ix tu re: N 2 :C O :H 2 = 4 0 :20 :4 0 ; P = 1 a tm ; T = 30 0 K
Рис.1. Баланс энергии электронов в смеси N2:CO:H2 = 40:20:40; характерное значение приведенного
электрического поля ВВРАД находится в диапазоне E/N=1-4 10-16 В см2
Fig. 1. Electron energy balance for N2:CO:H2 = 40:20:40 mixture
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
3 0 0 0
3 5 0 0
4 0 0 0
Tem
per
atu
res,
K
0 0 .5 1 1 .5 2z , cm
T N 2
T
M ix tu re: N 2 :C O :H 2 = 4 0 :2 0 :0 ; W = 2 4 5 W ; Q = 5 0 0 N l/h
T C O
T H 2
v ib
v ib
v ib
0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5V ib r a tio n a l lev e l
-1 0
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
Vib
rati
onal
dis
trib
utio
n fu
ncti
on, l
g(f(
v))
-1 0
-9
-8
-7
-6
-5
-4
-3
-2
-1
0M ix tu re: N 2 :C O :H 2 = 4 0 :2 0 :0 ; W = 2 4 5 W ; Q = 5 0 0 N l/h
z= 0 m m
2
6
1 2
2 0
2
61 2
2 0
- N 2
- C O
Рис.2. Изменение поступательной и колебательных температур и эволюция колебательных функций распределения CO и N2 вдоль оси разряда
Fig.2. Distribution of translational and vibrational temperatures and evolution of vibrational distribution functions of CO and N2 along the discharge axis:
P=1 atm; mixture: N2:CO:H2=40:20:0; W=245 W; Q=500 Nl/h; Ldis=2 cm
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
3 0 0 0
3 5 0 0
4 0 0 0T
emp
erat
ure
s, K
0 0 .5 1 1 .5 2z , cm
T N 2
T
M ix tu re: N 2 :C O :H 2 = 4 0 :2 0 :1 ; W = 2 4 5 W ; Q = 5 0 0 N l/h
T C O
T H 2
v ib
v ib
v ib
0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5V ib r a tio n a l le v e l
-1 0
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
Vib
rati
onal
dis
trib
utio
n fu
ncti
on, l
g(f(
v))
-1 0
-9
-8
-7
-6
-5
-4
-3
-2
-1
0M ix tu re: N 2 :C O :H 2 = 4 0 :2 0 :1 ; W = 2 4 5 W ; Q = 5 0 0 N l/h
z = 0 m m
26
1 2
2 0
2
1 2
2 0
6
- N 2
- C O
Рис.3. Изменение поступательной и колебательных температур и эволюция колебательных функций распределения CO и N2 вдоль оси разряда
Fig.3. Distribution of translational and vibrational temperatures and evolution of vibrational distribution functions of CO and N2 along the discharge axis:
P=1 atm; mixture: N2:CO:H2=40:20:1; W=245 W; Q=500 Nl/h; Ldis=2 cm
0
5 0 0
1 0 0 0
1 5 0 0
2 0 0 0
2 5 0 0
3 0 0 0
3 5 0 0
4 0 0 0
Tem
per
atu
res,
K
0 0 .5 1 1 .5 2z , cm
T N 2
T
M ix tu re: N 2 :C O :H 2 = 4 0 :2 0 :4 0 ; W = 2 4 5 W ; Q = 5 0 0 N l/h
T C O
T H 2
v ib
v ib
v ib
0 5 1 0 1 5V ib r a tio n a l le v e l
-1 0
-9
-8
-7
-6
-5
-4
-3
-2
-1
0
Vib
rati
onal
dis
trib
utio
n fu
ncti
on, l
g(f(
v))
-1 0
-9
-8
-7
-6
-5
-4
-3
-2
-1
0M ix tu re: N 2 :C O :H 2 = 4 0 :2 0 :4 0 ; W = 2 4 5 W ; Q = 5 0 0 N l/h
z = 0 m m
2
61 2
2 0
2
- N 2
- C O
Рис.4. Изменение поступательной и колебательных температур и эволюция колебательных функций распределения CO и N2 вдоль оси разряда]
Fig. 4. Distribution of translational and vibrational temperatures and evolution of vibrational distribution functions of CO and N2 along the discharge axis:
P=1 atm; mixture: N2:CO:H2=40:20:40; W=245 W; Q=500 Nl/h; Ldis=2 cm
Atmospheric-pressure high-voltage discharge (APHVD) Atmospheric-pressure high-voltage discharge (APHVD)
DesignationDesignation
• Carbon nanomaterials Carbon nanomaterials fabricationfabrication
Входгазовой
смесиАнод
Перемещаемыйкатод
Кварцеваятрубка
Выход водородаи других продук-тов конверсии
- 2 6 кВ
Fig. 1. Diagram of experimental setup:
APHVD for carbon nanomaterials synthesis APHVD for carbon nanomaterials synthesis
Current, mА
Voltage, kV
b)
2
2,5
3
3,5
4
4,5
40 60 80 100 120 140 160 180 200
30 mm
20 mm
Interelectrode Gap
2
2,5
3
3,5
4
4,5
40 60 80 100120140160180 200
30 mm
20 mm
a)
Current, mА
Voltage, kV
Interelectrode Gap
Voltage-current characteristics of APHVD:
a) Methane-air mixture;
b) Gas mixture after methane-to-hydrogen conversion device.
CARBON NANOTUBES FABRICATION UNDER CARBON NANOTUBES FABRICATION UNDER NONEQUILIBRIUM CONDITIONS IN APHVDNONEQUILIBRIUM CONDITIONS IN APHVD
CO(v) + CO(w) CO2 + CEv + Ew 5.5 eV
Reactants А + В С + D Products
Ea
)( 0 TTk
E
E
a
aeN
Recuperation process: - energy exchange through «intermediate agent» (filtrational superadiabatic combustion)
T0
Energy saving
105
oTT
T
activationenergy
Caloric effect of reaction
Thermally Nonequilibrium Processes for CO productionThermally Nonequilibrium Processes for CO production
Hydrocarbons to Hydrogen-CO conversion under nonequilibrium Hydrocarbons to Hydrogen-CO conversion under nonequilibrium superadiabatic filtration combustion superadiabatic filtration combustion
Filtration combustion reator Filtration combustion reator
1. Kerosene/air atomizer;2. Mixing chamber;3. Spark-plug;4. Quartz reactor with ceramic
bed;5. Electric heater;6. Condenser;7. Condensate trap.
1
2
3
4
5
6 7
HH22, CO, CH, CO, CH44, CO, CO22 content in products of incomplete kerosene content in products of incomplete kerosene
oxidation reaction oxidation reaction
1 – теоретически оптимальное значение степени эквивалентности для реакции неполного окисления
1
CH4
CO2
2.0 2.4 2.8 3.2 3.6 4.0
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
Мол
ьная
дол
я
1
H2
CO
Мол
ьная
дол
я
2.0 2.4 2.8 3.2 3.6 4.0
0.12
0.14
0.16
0.18
0.20
0.22
0.24
Степень эквивалентностиСтепень эквивалентности
Effect of equivalence ratio on kerosene-to-hydrogen conversion Effect of equivalence ratio on kerosene-to-hydrogen conversion efficiency efficiency
Сте
пен
ь к
онве
рси
и к
ерос
ин
а в
водо
род
Степень эквивалентности
2.0 2.5 3.0 3.5 4.0
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Fig.3. TEM image of several ropes of nanofibres. Scale bar 100 nm. Graphite cathode. Gas mixture after methane-to-hydrogen conversion device.
Fig. 4. TEM image of several ropes of nanofibres. Scale bar -100 nm. Zirconium cathode. Methane-air mixture.
Fig. 5. TEM image of multi-walled nanotubes. Scale bar - 50 nm. Zirconium cathode. Gas mixture after methane-to-hydrogen conversion device.
.
PROCESS SCALE-UPPROCESS SCALE-UP
• SCALE-UP OF HYDROCARBONS TO CO-HYDROGEN CONVERSION
• SCALE-UP OF THE ATMOSPHERIC PRESSURE DISCHARGE
Hydrogen –CO mixtures Production Facility
Plasma Hall accelerator for carbon nanomaterials fabricationPlasma Hall accelerator for carbon nanomaterials fabrication
i
ifz = j*Br
B
e
e
j
Физическая модель
Plasma Hall accelerator for carbon nanomaterials fabricationPlasma Hall accelerator for carbon nanomaterials fabrication
CARBON NANOMATERIALS FABRICATED CARBON NANOMATERIALS FABRICATED UNDER NONEQUILIBRIUM CONDITIONSUNDER NONEQUILIBRIUM CONDITIONS
0
10
20
30
40
50
60
70
0 50 100 150 200 250
Деформация, %
Нап
ряж
ение
, МП
а
а
0.5% CNM
1% CNM
3
4
1
2
COMPOSITES WITH CARBON NANOMATERIALSCOMPOSITES WITH CARBON NANOMATERIALS
Fig.2. Strain curves:1 – initial PA-6;2 – PA-6 stabilized with 0.15 mass % of irganox B-11713 – Stabilized PA-6 filled with carbon nanomaterial (CNM) – 0.5 mass %4 – Stabilized PA-6 filled with carbon nanomaterial (CNM) – 1 mass %
- up to 20% increase of strength parameters during stretching - broadening of strain range (from ~14% to 18-22%) to the instant of forced ductility development (neck formation), i.e. ability to withstand higher strains at load close to yield point.- reduction of tensile strain (4-6 times) (it is related to the presence of large (up to 20 m) particles of SiO2)
A
B
Fig. 1. Photo of polymer specimens:A – initial material, polyamide (PA-6);
B – composite obtained by adding 0.5% carbon nanomaterial to initial PA-6.
Strain,%
Ten
sion
, MP
a
POLYAMIDE FILMSPOLYAMIDE FILMS
Polyamide (PA-6) films filled with 0,1 % carbon
nanomaterial before and after thermal treatment at 185 ˚C
Strength limit, МПа
Before thermal treatment
After thermal treatment
Initial PA-6
PA-6 filled with nanomaterial
Relative extension near point of break
NEUTRAL OPTICAL FILTERSNEUTRAL OPTICAL FILTERS
Filter with CNM
Ordinary filter
400 750
Tra
nsm
issi
on f
acto
r d
evia
tion
, T
, %
Filters with CNM
K =
91%
K =
82%K
= 6
9%
K =
1% K =
4%
K =
4 0
%
K =
54%
Ordinary filters
Fig. 2. Transmission factor vs wave length
K = 4% K = 69% K = 91%
Fig. 1. Pictures of neutral optical filters with CNM additives
Fig. 3. Transmission factor deviation T for filters with different light-transmission factor T
Carbon Nanotubes Applications in Atomic Force Microscope
OUR AFM DEVISES
NEW
E-mail [email protected]
NANOTOP is an atomic force microscope (AFM)
in a complex with hardware and software necessary to
analyse topography and micromechanical properties
of a surface with nanometer resolution
A design of Nanotechnologyof Lab. Of HMTI NASB
Manufactured by Chemical Physics Technologies Ltd.
NANOTESTER-LV
+Video System
(SNU Precision Co.)
NANOTOP-203 NANOTOP-204
ConclusionsConclusionsNonequilibrium atmospheric pressure plasma based technologies were developed for mass production of carbon nanomaterials;
Energy cost of MWCNT production was reduced to 100 kWh/kg based on the natural gas as the raw material;
The reliable operation of experimental facility with MWCNT production up to 10g/h based on different hydrocarbons as the raw materials was demonstrated;
The design of the pilot plant with MWCNT production up to 100g/h is ready for commercialization.