Next Generation Low GWP Refrigerant HFO-1234yf

Part 2
Honeywell / DuPont Joint Collaboration

Barbara Minor Mark Spatz

DuPont Honeywell

January 23, 2008

ASHRAE Meeting, New York, NY

1 January 30, 2008

 Agenda

• Flammability Properties
– LFL-UFL
– Minimum ignition energy
– Burning velocity
– Flammability indices
• Flammability Tests and Modeling
– Static ignition tests with various sources
– Flame extension test
– CFD modeling
• Risk Assessments

2 January 30, 2008

 Refrigerant Flammability Properties

• Is the refrigerant flammable?

– LFL – lower flammability limit
– UFL – upper flammability limit

• What is the probability of an ignition source being

present of sufficient energy to cause an ignition?
– Minimum ignition energy
– Autoignition temperature

• What is the impact (damage potential) if an ignition

occurs?
– Burning velocity
– Heat of combustion

3 January 30, 2008

 1234yf Flame Limits (LFL and UFL)

LFL Values LFL* UFL* Delta

(vol%) (vol%) (vol%)
Ammonia 15 vol.%
HFC-32 14.4 vol.%
Propane 2.2 10.0 7.8
R152a 3.9 16.9 13.0
R32 14.4 29.3 14.9
Ammonia 15 .0 28.0 13.0
1234yf 6.5 12.3 5.8
1234yf 6.5 vol.% * Measured at 21°C

ASTM E681 Apparatus

Methane 4.6 vol.% • ASTM E-681 in US
Air In Refrigerant In – 2001 version cited by
HFC-152a 3.9 vol.%
ASHRAE
(12 liter flask, spark ignition)
Ethylene
3.0 vol.%
Oxide –Flame must reach the wall
Acetylene 2.5 vol.% and exhibit > 90 degree
angle
Propane 2.2 vol.% Spark Ignition
Stirrer
Gasoline 1.3 vol.%

More
Flammable
1234yf Has Narrowest Flammable Region
4 January 30, 2008
 1234yf Minimum Ignition Energy

• ASTM E-582 apparatus with 1 liter vessel

MIE, mJ
– Tested HFO-1234yf up to 1,000 mJ which
was maximum energy available Methane 0.47
– No ignition occurred Propane 0.25
HFC-152a 0.38
• “Wall-effects” can quench flame propagation HFC-32 >30, <100
suppressing ignition
Gasoline 0.29
– “Wall-effects” have greater significance with
difficult to ignite materials (like some Ammonia 680
halocarbons), especially in smaller vessels 1234yf > 1000
– Important to use appropriately sized test
vessels for halocarbon flammability testing ASTM E-582 MIE Apparatus
• 1 liter spherical vessel
• Retested in 12 liter vessel up to 1,000 mJ • Metal electrodes, variable
– Still no ignition occurred gap; vary gap to > ignition
quenching distance
• Sight glass to monitor ignition
& propagation

1234yf Is Very Difficult To Ignite . . . Similar To Ammonia

5 January 30, 2008

 1234yf Flammability Properties

Ignition Source
1000
Flames.
1234yf Chemical sources.
Propagating brushes.
Minimum Ignition Energy, mJ

100

in g sk
s Ri
a
cre ility Personnel spark limit
10 In ab
m m
Fla
Iso-Butane Mechanical sparks.
1 Stray current sparks.
Methane Ungrounded con-
ductors.
Propane
152a
0.1 A glowing cigarette
Gasoline Will not ignite methane
(A.D. Little) Static discharge from
clothing
Acetylene
0.01
0 1 2 3 4 5 6 7
Lower Flame Limit, vol.%
6 January 30, 2008
 Burning Velocity

ISO 817 Burning Velocity Apparatus HFC-32 1234yf

150 cm tube

38 mm internal
diameter

• 18 vol.% in air • 8 vol.% in air - stoichiometric

stoichiometric • Flame propagates < 8 cm
• Propagates entire length at low velocity
of the tube – 150 cm • Wall effects extinguish
the flame

Burning Velocity Data

Propane 152a NH3 32 1234yf

BV,
46 23 7.2 6.7 1.5*
cm s-1

Video area Ignition Source *3 liter spherical method

15 kV, 30 mA
power for 0.3 s.

1234yf Burning Velocity Less Than That Of HFC-32

7 January 30, 2008
 Flammability Indices

Molecule R F RF RF2 Flammability Index

kJ/g (kJ/mol)(m/s)
1. R proposed by O. Kataoka ,
1234yf 0.97 0.27 3.6 0.6* ISO TC86/SC8/WG5, Feb 2000
2. F proposed by Kondo,
Ammonia 1.45 0.27 6.8 1.5 J. Hazard. Mater. 2606 (2001) 1-16
32 1.31 0.33 4.6 2.3 3. RF proposed by Kondo,
J. Hazard. Mater. A93 (2002) 259-267
152a 1.78 0.5 16.6 17.9
4. RF2 proposed by Kondo, Seminar 10,
Propane 1.99 0.55 56.7 37.2 ASHRAE, June 2003.

*Assumes a burning velocity of 1.5 cm s-1

Cst
R= Cst = Stoichiometric flammable composition in air, vol.%
LFL
 LFL  Q = Heat of Combustion per one mole
F = 1−  
 UFL  Qst = Heat of Combustion per one mole of the
  UFL   Q Stoichiometric mixture, kJ/mol
RF =    − 1 ×
  LFL   M Su = Burning speed in Meters/Second
RF 2 = {( (UFL × LFL ) − LFL ) / LFL}× Qst × Su M = Molecular weight

1234yf Has Lowest Flammability Index

8 January 30, 2008
 Static Ignition Test Setup
Vacuum Pressure
Connection Indicator
Refrigerant/Air
Connection

Rubber Stopper
“Overpressure Relief”

Pressure
Transducer

Igniter
8.5 Liter
Glass Tube

9 January 30, 2008

 Static Ignition Tests at Worst Case Conditions

- 8.5 liter chamber with well mixed conditions

- Stoichiometric worst case refrigerant/air concentrations
- Room temperature, 50% relative humidity for R152a, R32
and HFO-1234yf; dry for ammonia to prevent reaction with
water

Test R152a R-32 Ammonia 1234yf

Cigarette No Ign No Ign No Ign No Ign

Glowing Hot Wire Ign No Ign No Ign No Ign

Butane Lighter Ign Ign Weak Ign Weak Ign
Fused Wire 100-300 J (worst
case) Ign Ign Ign Ign

HFO-1234yf Is More Difficult To Ignite Than R32 and

R152a, Similar To Ammonia
10 January 30, 2008
 1234yf Aerosol Flame Extension Test

ASTM Method D 3065-01 Vapor

• Flame Extinguished

Mist

• Aerosol flammability test • Flame Extinguished

• Referenced by IATA & US DOT
• Aerosol (liquid + vapor) spray through a
candle flame from a distance of 15 cm
• Flame extension measured Stream

• Flame Extinguished

1234yf Is More Difficult To Ignite In Dynamic Situations

11 January 30, 2008
 CFD Modeling HFO-1234yf vs R-152a

• Used Computational Fluid Dynamics model to simulate

a large evaporator leak in a vehicle
– Internal volume = 3.1 m3
– 550 g refrigerant charge
– 6 passengers
– 100% recirculation
– Low fan speed – 60 cfm

• Modeled activation of a squib valve 10 seconds after

the leak begins

12 January 30, 2008

 1 Second After Leak

Top View Side View 152a vol.%

16% UFL
14%
12%
152a 10%
8%
6%
4% LFL

1234yf vol.%
12% UFL
11%
10%
1234yf
9%
8%
7% LFL

13 January 30, 2008

 5 Seconds After Leak

Top View Side View 152a vol.%

16% UFL
14%
12%
152a 10%
8%
6%
4% LFL

1234yf vol.%
12% UFL

11%
10%
1234yf
9%
8%
7% LFL

14 January 30, 2008

 9 Seconds After Leak

Top View Side View 152a vol.%

16% UFL
14%
12%
152a 10%
8%
6%
4% LFL

1234yf vol.%
12% UFL
11%
10%
1234yf
9%
8%
7% LFL

15 January 30, 2008

 11 Seconds After Leak
Squib Activated at 10 Seconds

Top View Side View 152a vol.%

16% UFL
14%
12%
152a 10%
8%
6%
4% LFL

1234yf vol.%
12% UFL
11%
10%
1234yf
9%
8%
7% LFL

16 January 30, 2008

 13 Seconds After Leak

Top View Side View 152a vol.%

16% UFL
14%
12%
152a 10%
8%
6%
4% LFL

1234yf vol.%
12% UFL
11%
10%
1234yf
9%
8%
7% LFL

17 January 30, 2008

 CFD Modeling Conclusions

• HFO-1234yf flammability envelope was significantly smaller

than 152a
• HFO-1234yf flammable region was limited to a small volume at
the exit of the vents
• Flammable HFO-1234yf / air compositions did not collect or
pool in other regions of the car
• This significantly reduces the possibility that an ignition source
with sufficient energy can be present in the flammable region
during a leak
• Squib activation eliminated the HFO-1234yf flammable region
within one second; 152a flammable region remains

HFO-1234yf Flammability Risk Significantly Reduced

Versus 152a
18 January 30, 2008
 Risk Assessments

For most fires to happen, fuel and air at the right concentration, and an
ignition source, with a sufficient energy level must co-exist at the same
place and in the same time.

Several risk assessments based on fault tree analysis are underway in US,
Japan and Europe utilizing inputs of modeling and leak experiments

Release Experiments
 Cabin and underhood
 Normal operation and crash condition
 Service

CFD modeling to visualize concentration distribution

for various scenarios.
R152a

1234yf

19 January 30, 2008

 HFO-1234yf Summary

• Excellent environmental properties

– Very low GWP, Zero ODP, Good LCCP
– Atmospheric chemistry determined
• Low toxicity, comparable with 134a
– Low acute and chronic toxicity
– Significant testing completed
• System performance very similar to 134a
– Excellent COP and Capacity, no glide
– Thermally stable and compatible with 134a components
– Potential for direct substitution of 134a
• Mild flammability (manageable)
– Flammability properties significantly better than 152a;
– potential for “A2L” ISO 817 classification versus “A2” for 152a
– Significantly different vehicle leak behavior than 152a
– Potential to use in a direct expansion A/C system; better performance, lower
weight, smaller size than a secondary loop system

20 January 30, 2008