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HAN based green propellant- Application and its
Combustion Mechanism -
Toshiyuki KATSUMI and Keiichi
HORI(ISAS/JAXA)
HAN-based liquid propellant
Hydroxyl Ammonium Nitrate (NH2OH ・HNO3)
High Oxidizability Low Toxicity High Deliquescent
High Density Low Freezing Point
Water Solution Liquid Oxidizer Monopropellant
Hydrazine
HAN-based propellant(SHP163)
Density ρ [×103 kg/m3] at 20 ˚C 1.0 1.4
Freezing temperature [˚C] 1.4 -68
Specific Impulse Isp** [s] 233 276ρ ・ Isp** [×103 s*kg/m3] 233 386
Toxicity High Low* SHP163: HAN/Ammonium Nitrate/Water/Methanol=95/5/8/21 (mass
ratio)** Nozzle area ratio (Ae/At);50, CF;1.875, Combustion chamber pressure;
0.7MPa
ρ ・ Isp of HAN-based propellant is approximately 70% higher than Hydrazine
Comparison of HAN-based solution with Hydrazine
0.1
1
10
100
1000Sample #1 (95/5/8/0)
1 10
RE
GR
ES
SIO
N R
AT
E /
mm
/s
PRESSURE / MPa
5 73
Control
Burning rate
0.1
1
10
100
1000Sample #1 (95/5/8/0)Sample #2 (95/5/8/8)
1 10
RE
GR
ES
SIO
N R
AT
E /
mm
/s
PRESSURE / MPa
5 73
Control SHP069
Control HAN/AN/Water/Methanol = 95/5/8/0SHP069 HAN/AN/Water/Methanol = 95/5/8/8SHP163 HAN/AN/Water/Methanol = 95/5/8/21
0.1
1
10
100
1000Sample #1 (95/5/8/0)Sample #2 (95/5/8/8)Sample #3 (95/5/8/21)
1 10
RE
GR
ES
SIO
N R
AT
E /
mm
/s
PRESSURE / MPa
5 73
Control SHP069 SHP163
• Hydrodynamic instability triggers the jump of the burning rate to very high rate region• Methanol addition shifts the critical pressure to higher pressure.
Combustion mechanism has not been clarified
AN and methanol are eliminated
1
10
100
1000
1 10Pressure [MPa]
Line
ar b
urni
ng r
ate
[mm
/s]
3 5 72 4 6 8 9
80mass%
77.5mass%
64mass%
50mass%
95mass%
85mass%
Burning rates of aq. solutions
82.5mass%
Crystal*
64mass%*
*B. N. Kondrikov, V. E. Annikov, V. Yu. Egorshev, and L. T. De Luca, “Burning of Hydroxylammonium nitrate”, Combustion, Explosion and Shock waves, Vol.36,No.1 ,2000
The linear burning rate has the peak at approximately 80mass% of HAN concentration
1
10
100
1000
1 10Pressure [MPa]
Line
ar b
urni
ng r
ate
[mm
/s]
3 5 72 4 6 8 91
10
100
1000
1 10
95mass%
85mass%
82.5mass%
80mass%
77.5mass%
64mass%
50mass%
Crystal by De Luca
3 5 72 4 6 8 9
Zone3
Zone2
Zone1
0 5 10 15300
400
500
600
700
800
Tem
pera
ture
T /
K
Distance x / mm
0 5 10 15300
400
500
600
700
800
Tem
pera
ture
T /
K
Distance x / mm
High burning rate
Low burning rate
The linear burning rates are classified to three zones
Objective
Combustion Model of HAN-based propellant solution
Combustion model of HAN aqueous solution
95mass% solution 80mass% solution
T
Tf
Liquid phase Gas phase
Two-phase
Reaction zone
T
Two-phaseLiquid phase
Tbp Tbp
The combustion wave structure of HAN aq. solution
95mass% solution 80mass% solution
T
Tf
Liquid phase Gas phase
Two-phase
Reaction zone Reaction zone
T
Two-phaseLiquid phase
Tbp Tbp
Combustion wave structure changes by the water content
The combustion wave structure of HAN aq. solution
Two-phase region
1. Fine bubbles are generated in front of the combustion wave
2. Chemical reaction starts in the bubble
Reaction zone
Two-phaseLiquid phase
High rb mode
Two-phase region
1. Fine bubbles are generated in front of the combustion wave
2. Chemical reaction starts in the bubble3. Significant superheat (T) is generated
Reaction zone
Two-phaseLiquid phase
T
High rb mode
Two-phase region
1. Fine bubbles are generated in front of the combustion wave
2. Chemical reaction starts in the bubble3. Significant superheat (T) is generated4. Rapid nucleation is caused by superheat
T
Reaction zone
Two-phaseLiquid phase
High rb mode
Reaction zone
Two-phaseLiquid phase
High rb modeTwo-phase region
1. Fine bubbles are generated in front of the combustion wave
2. Chemical reaction starts in the bubble3. Significant superheat (T) is generated4. Rapid nucleation is caused by
superheat5. High rb mode is established
Nucleation rate may determine the burning rate
Superheat & Nucleation rate
TMpi
RTr
ffg
SAT
2* 2
SATg TTT
hkTg / **
3
4)( rrG
gkTrGNedt
dn )( *
T; superheatTg; vapor temperatureTSAT; saturation temperaturedn/dt; nucleation rateN; number of molecules per unit volumek; Boltzmann constanth; Plank’s constantr*; radius of the vapor nucleus; surface tensionR; universal gas constantifg; latent heat of vaporizationM; molecular weightpf; pressure in liquid space
Tg TSAT
Liquid Bubble
,
1.E-09
1.E-08
1 10
Pressure (MPa)
r* (
m)
2 3 4 5 6 7 8 9
5E-09
Tg=900KTg=800K
Tg=1300K
Tg=1200K
Tg=1100KTg=1000K
1.E-09
1.E-08
1 10
Pressure (MPa)
r* (
m)
2 3 4 5 6 7 8 9
5E-09
Tg=900KTg=800K
Tg=1300K
Tg=1200K
Tg=1100KTg=1000K
r*min=2x10-9m
Radiuses of vapor nucleuses
(10A)
Parameter; Pressure1~8MPa
Gas temperature800~1300K
Nucleation rate (dn/dt)
1E+00
1E+02
1E+04
1E+06
1E+08
1E+10
1E+12
1E+14
1E+16
1E+18
1E+20
1E+22
1E+24
1E+26
1E+28
1E+30
1 10Pressure [MPa]
Nuc
leat
ion
rate
[m
-3s-
1]
2 3 4 5 6 7 8 9
Tg=1100KTg=900K
Tg=1000KTg=800K
Tg=1200K
Tg=1300K
Parameter; Pressure1~8MPa
Gas temperature800~1300K
r*min=2x10-9m
1E-501E-471E-441E-411E-381E-351E-321E-291E-261E-231E-201E-171E-141E-111E-081E-051E-021E+011E+04
1 10
Pressure (MPa)
dv/dt
(m3 /s
)
Tg=1100K Tg=900K
Tg=1000K
2 3 4 5 6 7 8 9
Tg=800K
Tg=1200K
Tg=1300K
dv/dt (4/3r*3dn/dt)1000mm/s
1mm/s
Linear burning rate
In Zone2, bubble nucleation rate governs the burning rate.
1
10
100
1000
1 10Pressure [MPa]
Line
ar b
urni
ng r
ate
[mm
/s]
3 5 72 4 6 8 9
80mass%
77.5mass%
82.5mass%
64mass%
50mass%
dv/dt (4/3r*3dn/dt)
1E-501E-471E-441E-411E-381E-351E-321E-291E-261E-231E-201E-171E-141E-111E-081E-051E-021E+011E+04
1 10
Pressure (MPa)
dv/dt
(m3 /s
)
Tg=1100K Tg=900K
Tg=1000K
2 3 4 5 6 7 8 9
Tg=800K
Tg=1200K
Tg=1300K
1000mm/s
1mm/s
Linear burning rate
80-50mass%; The gas temperature in bubbles may be lower than 80 mass% aq. solution because of higher water content. The nucleation and burning rates become lower.
95-80mass%; The gas temperature in bubble may be lower than 80 mass% aq. solution, as the two-phase region is relatively short. The nucleation and apparent burning rates become lower.
Combustion mode in Zone3
(4) Expansion into liquid phase (5) Expansion stops
(3) Concentration of reactive gas into concave area
Surface propagation rate increases rapidly by the local disturbance
(2) Local disturbance(1) Stable combustion
wave
Comparison of combustion wave structure
1
10
100
1000
1 10Pressure [MPa]
Line
ar b
urni
ng r
ate
[mm
/s]
3 5 72 4 6 8 9
Zone3
Zone2
Zone1
Propellant solution
0.1
1
10
100
1000Sample #1 (95/5/8/0)Sample #2 (95/5/8/8)Sample #3 (95/5/8/21)
1 10
RE
GR
ESS
ION
RA
TE
/ m
m/s
PRESSURE / MPa
5 73
Control SHP069 SHP163
Aqueous solution
The jump mechanism of burning rate to high rate region is not clarified
Low rb
High rb
Combustion wave structures of propellant solutions are similar to aqueous solution in
each burning rate zone
Phenomena of Burning Rate Jumping
Transition Process
Liquid
Liquid(4) New bubbles develop quickly
(5) Extremely high burning rate is established
Liquid New BubbleLiquid(1) Stable
combustion wave propagates
(3) New fine bubble are generated
Liquid(2) Brown bubble invade into liquid phase
Hydrodynamic instability is the trigger to jump to extremely high
burning rate region
Hydrodynamic instability - 1
◆Margolis model; extended model of Landau/Levich instability
Stable at high pressure, and at low methanol content Our results; Unstable at high pressure and at low methanol content
Estimation result is opposite tendencies to
our results
KaMaSu
- SuSu
(l)
(s)(l) Su(s); Burnign rate of stretched flame
Su(l); Laminar burning rate
Ka; Flame stretch ratio
Markstein number (Ma)
Number Lewis ;Numberdovich Zel';,
1ln
1
1
2
1ln
1
20
1
0
D
aLe
T
TTT
dxx
xLeMa
s
addbu
By Clavin P., Energy Combust. Sci., vol.11, pp.1-59, 1985
Markstein number (by asymptotics)
◆ Flame stretch effect
Lewis number effect; out of consideration
(Lewis number; no pressure dependency)
Hydrodynamic instability - 3
4
4.5
5
5.5
6
6.5
7
7.5
0 2 4 6 8 10Pressure [MPa]
Mar
kste
in N
umbe
r
ControlSHP069SHP163
Unstable at high pressure, and at low methanol content Our results; Unstable at high pressure and at low methanol content
Ma=Ma,cr
Estimation results supports our results0.1
1
10
100
1000Sample #1 (95/5/8/0)Sample #2 (95/5/8/8)Sample #3 (95/5/8/21)
1 10
RE
GR
ESS
ION
RA
TE
/ m
m/s
PRESSURE / MPa
5 73
Control SHP069 SHP163
3.3MPa5.0MPa
6.6MPa
Hydrodynamic instability of propellant solutions is affected by
flame stretch and determines the jump
pressure.
Application to thruster
Development of HAN-based Monopropellant Thruster
ObjectiveObjective
HeaterHeaterHeaterHeater
CatalystCatalystCatalystCatalyst
Burning process1.Monopropellant is injected into the preheated catalyst bed.2.Chemical reaction of monopropellant occurs at the catalyst bed.3.Gas products burn thoroughly in the combustor.4.Combustion product gas is exhausted through the nozzle.
Propellant; SHP163Catalyst; S405
PropellantPropellantPropellantPropellant
Free fall test 1/2
Launch
[email protected] Y=0 sec
Y+20 secStart
Y +50 secFinish
Thrusters burnfor 30 seconds
Sequence
HAN-based thruster system
ObjectiveObjectivePretest of supersonic vehicle test flight • Balloon operation• Attitude control by N2 gas jets• HAN thrusters help the acceleration at free fall
Supersonic vehicle mock-up
Flight system
Free fall test 2/2
Catalyst bed
Injector
Combustion chamber
Pressure sensor
Thermocouple
Nozzle
Diameter; 75 mm Length; 992.5 mm
Thruster
Thruster
Valve
Propellant Tank
Static firing testSimulated environmental test (Vacuum and Low temperature)
• Thruster burned stably for 30 seconds in simulated condition
Static firing test (movie)
Result of free fall test
• Thruster burned well for 30 seconds in the flight• Density*Isp is approximately 1.46 times higher than the hydrazine• This results show the potential for the application to space programs
Specific impulse; 230 secCombustion efficiency; 0.88
Summary -Combustion mechanism-
• Bubble nucleation rate by superheat governs the apparent linear burning rate in very high burning rate zone.
• The water content dominates the burning rate zone in the case of aqueous solutions.
• The hydrodynamic instability determines the burning rate zone in the case of propellant solutions.
Summary -Application to thruster-
• Flight system is developed and burnt for 30 seconds successfully in vacuum and -50 C
• Isp is approximately 230 seconds
• The high potential of HAN-based thruster for the application to space programs was shown