The miracles ofscience-
`
`Honeywell
`
`HFO-1234yf
`Low GWP Refrigerant Update
`
`Honeywell I DuPont Joint Collaboration
`
`Mark Spatz
`
`Honeywell
`
`Barbara Minor
`
`DuPont
`
`International Refrigeration and Air Conditioning Conference at Purdue
`
`

`
`The miracles ofscience"
`
`Background
`
`Honeywell
`
`- DuPont And Honeywell Have Identified HFO-
`1234yf (CF3CF=CH2) As The Preferred Low
`GWP Refrigerant Which Offers The Best
`Balance Of Properties And Performance
`
`- Other Auto Industry Options Have Certain
`Limitations
`
`- CO2: complexity, energy efficiency and requires
`mitigation
`
`— 152a / secondary loop: performance, size and
`weight
`
`

`
`The miracles ofsciencer
`
`HFO-1234yf Summary
`
`Honeywell
`
`- Excellent environmental properties
`— Very low GWP of 4, Zero ODP, Favorable LCCP
`
`— Atmospheric chemistry determined and published
`
`- Low toxicity, similar to R-134a
`
`— Low acute and chronic toxicity
`
`— Significant testing completed
`
`- System performance very similar to R-134a
`
`— Excellent COP and Capacity, no glide
`
`- From both internal tests and OEM tests
`
`— Thermally stable and compatible with R-134a components
`
`— Potential for direct substitution of R-134a
`
`- Mild flammability (manageable)
`— Flammability properties significantly better than 152a; (MIE, burning velocity, etc)
`
`— Potential for “A2L” ISO 817 classification versus “A2" for 152a based on AIST data
`
`— Potential to use in a direct expansion A/C system - better performance, lower
`weight, smaller size than a secondary loop system
`
`

`
`‘ HFO-1234yf Properties
`
`The miracles ofscience‘
`
`Honeywell
`
`123434 Bi
`Properties
`-29°C
`-26°C
`Boiling Point, Tb
`95°C
`102°C
`Critical Point, Tc
`0.673
`0.665
`Pvap, MPa (25°C)
`2.47
`2.63
`Pm, MPa (aooc)
`Liquid Density, kg/m3(25°C) 1094
`1207
`Vapor Density, kg/m3 (25°C)
`37.6
`32.4
`
`35
`
`Va - or Pressure
`
`1 234”
`°"s°F=°"'2
`
`F33
`\
`c:c|-|2
`/
`
`F
`
` 2.5
`
`inN
`
`Pressure,MPa
`
`

`
`Honeywen
`4 Thermodynamic Analysis
`
`
`ical MAC Condition ”"””""’°‘°""""‘°' T
`
`nsnywm’) B8
`porDe
`
`-I-F0-1234y1
`'—R-1348
`
`3s383‘88§
`
`3
`
`(0AatQ‘#003
`
`-200kJAO.3-1.WkMQ-K
`
`Enthalpy (lulkg)
`
`

`
`Honeywell
`
`4 T
`
`he miracles ofscience"
`
`
`
`Excellent Environmental Properties
`
`°ODP=0
`
`- 100 Year GWP = 4
`
`(GWP,34a = 1300)
`
`— Measurements completed & published:
`
`“Atmospheric Chemistry of CF3CF=CH,"
`Chemical Physics Letters 439 (2007) pp 18-22
`
`- Atmospheric lifetime = 11 days
`
`- Atmospheric chemistry measured
`
`— Atmospheric breakdown products are the
`same as for 134a
`
`— No high GWP breakdown products (e.g.
`NO HFC-23 breakdown product)
`
`— Results published in 2008
`
`- Good LCCP
`
`
`
`Avuhlio ovllm ya man ncuraaincl av‘!
`
`‘;;:’Sc3enceDi'ect
`cm-u:n_nm.¢u «mm-I; nu:
`
`ICAL
`CH
`cs
`pH
`LETTERS
`on an. -an-guy‘:
`
`Atmospheric chemistry of CF,CF=CH3: Kinetics and mechanisms
`of gas-phase reactions with Cl atoms. OH radicals. and 03
`0.1. Nidsm ~'. M5. Ju1ndi‘.MP.
`Sulbudn Aldl:n'cn -. MD. Hurley 5
`TJ. wamngo
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`nzrmlfqdgmogc
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`nbnu A-mm maul mu
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`l:co\d11hnnvy&1:nhnlhI-n “hum!
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`
`Asian
`1.4-. pm bgb ml... a—v.. u.~nu.— — an In .u-- ncio ncr*<.1u=:‘nusrur".
`hour-Gcr-nI...u1u+ani.Ir". nan-o+crcr=au.Qrn oznx -' 3'1-sJ¢\b"I" .- '-\I|'l'nv at
`lalfli
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`Ia-.c
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`.- :\Il7UcvnI|\' uquucu-at
`
`I.M
`
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`clluroharourtoni
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`
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`an nw,q|m:mn.o:)
`
`mi in can an (iv) nnosflen: rnplalnin R53
`nre npornd teen
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`Enprimn-ere pinned in I I40-inn Pyrex rumor
`nirfnad Ion Manson Sing It!)
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`to paouusmauny an-
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`pmtoylia alnolnxhl fibrin.
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`In the rdnfi“ me an-r"InnII.|Il|¢ fnllai if runimsnkr
`pin
`
`up
`
`

`
`‘
`
`The miracles ofscience‘
`
`Honeywell
`
`
`
`Significant Toxicity Information Available
`
`Test
`
`H F0-1234yf
`
`1 34a
`
`- Acute Lethality
`
`No deaths 400,000 ppm No deaths 359,700 ppm
`
`- Cardiac sensitization
`
`NOEL > 120,000 ppm
`
`NOEL 50,000 ppm
`LOEL 75,000 ppm
`
`- 13 week inhalation
`
`NOEL 50,000 ppm
`
`NOEL 50,000 ppm
`
`- Developmental (Rat)
`
`NOAEL 50,000 ppm
`
`NOAEL 50,000 ppm
`
`- Genetic Toxicity
`
`Not Mutagenic
`
`Not Mutagenic
`
`- 13 week genomic
`(carcinogenicity)
`
`Not active (50,000 ppm) Baseline (50,000 ppm)
`
`\/
`
`‘/
`
`J
`
`~/
`
`/
`
`J
`
`- Environmental Tox
`
`NOEL > 100 mg/L (Pass) NOEL > 100 mgIL (Pass) /
`
`

`
`“HEW
`
`The miracles ofscience"
`
`Honeywell
`
`ATEL Calculation
`
`Refrigerant
`
`ATEL (ppm)
`
`
`
`- ATEL (Acute Toxicity Exposure
`Limit) is a value used by
`standards organizations (e.g.
`ASHRAE 34) to reduce the risks
`of acute toxicity hazards in
`normally occupied spaces.
`
`-
`
`It is calculated from the acute
`
`toxicity data for a given
`refrigerant and provides an
`estimate of the maximum
`
`exposure limit for a short time
`period (e.g. 30 minutes)
`
`R-12
`
`R-1 34a
`
`R-1 52a
`
`18,000
`
`50,000
`
`50,000
`
`40,000
`
`
`
`
`
`101,000
`
`co,
`
`
`
`HFO-1234yf
`
`

`
`QIJEIHID
`
`The miracles ofscience‘
`
`System Bench Test Results H0|1e)’We||
`
`
`
`39o._.m>=m_¢m_
`
`%%%%%%%%%%%%.,..0000000000000
`
`.w.. .3
`a‘iu||l|mm!millllll2:
`yullllil
`mu!N|||'iG8-
`IllilllE
`
`IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII3.
`
` -
`
`r||
`
`_
`
`l
`
`I
`
`I
`
`.
`
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`
`03.09!
`
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`
`Do«.8:
`
`unéns
`
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`
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`
`on.8~:8#33
`
`03.2.3!
`
`onémuz
`
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`
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`
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`
`
`
`8......._
`
`oneE‘8run..._
`
`ureaw:8Ta:2
`
`u3.m2..
`
`095.0
`
`- No changes were made to system including TXV; Industry standard test conditions
`- Both Capacity and COP are generally within 5% of 1343 performance.
`- This was recently confirmed at two outside labs.
`- Lower compression ratio, low discharge temperature
`(12°C lower at peak conditions)
`- Further improvements likely with minor system optimization, for example:
`—
`Lower AP suction line and / or TXV optimization to maintain a more optimum supemeat.
`HFO-1234yf performance is comparable to 134a; further improvement
`
`
`
`
`
`
`

`
`Preliminary LCCP Analysis
`
`“°"°""'°"
`
`GM Model Using Bench Test Performance Results
`Relative to R-134a
`
`Average 15% Better LCCP Values; Up to 27% in Europe
`
`0
`
`o
`
`0000509887766
`//o/AAA/o/o/o/oAonooo0oo%505050
`
`55
`
`05
`
`

`
`The miracles ofscience"
`
`Honeywell
`
`
`
`1234yf: Excellent Plastics Compatibility
`ND8 PAG at 100°C for two weeks
`
`Rating 0 = best when weight gain < 1 and physical change = O
`1 = borderline when weight gain > 1 and < 10 and/or physical change upto 2
`
`

`
`The miracles of science‘
`
`Honeywell
`
`1234yf: Excellent Elastomers Compatibility
`ND8 PAG at 100°C for two weeks
`
`flu“
`jjnmazjjzmxxzz
`$-I|31z_j1j!-
`jiflfllnliji-Ii
`jEIIE?I11:K1ieZI1
`fl Bu Irubber -.111!-Z1
`
`"°°"'°“° jEZZ
`
`jfilfllnjll-KIT
`t Bu Imbber “II-Zlljfil
`
`Rating
`
`0 = best when weight gain < 1 and physical change = 0
`1 = borderline when weight gain > 1 and < 10 and/or physical change upto 2
`
`

`
`c,m,s,,,.,_,,,a_,._ Permeation HFO-1234yf vs R-134a "°“e3'We"
`
`Standard Veneer Hose
`
`ULEV Veneer Hose
`
`Results
`
`HFO-1234yf shows lower permeability values toward Veneer hoses compared to R134a.
`
`Remarks
`
`With the same gas concentration (0.6glcm3) the inner pressure with
`
`

`
`flllflfli
`
`The miracles ofscience-
`
`Honeywell
`
`
`
`Refrigerant Flammability Tests
`
`- Is it flammable? If yes, Flame Limits will exist.
`— 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?
`— Autoignition temperature
`
`— Minimum ignition energy (MIE)
`
`- What is the impact (damage potential) if an ignition
`occurs?
`
`— Heat of combustion
`
`

`
`‘ HFO-1234yf Flame Limits
`
`The miracles ofscience-
`
`Honeywell
`
`- HFO-1234yf flame limits measured using ASTM
`E681-04 T= 21°C : 6.2 vol.% to 12.3 vo|.%
`
`- Low LFL value -) more flammable
`
`- Wider UFL - LFL -) more flammable
`
`ASTM E681 Apparatus
`
`- ASTM E-681 in US
`
`A5,. In
`
`Ref”-9e,a,,t In
`
`— 2004 version cited by ASHRAE
`(12 liter flask, spark ignition)
`
`— Flame must reach the wall and
`
`(5 liter flask, match ignition)
`
`exhibit > 90 degree angle
`
`— 1985 version cited by SAE
`
`- A11 in EU
`— 5 cm x 30 cm Vertical tube
`.
`.
`.
`‘ 393"‘ '9"'t’°"
`— Flame travels up the tube
`
`
`
`
`Spark Ignition
`stirrer
`‘.“
`
`LFL Values
`
`Ammonia
`
`15vol.%
`
`HFC-32
`
`13.3voI.%
`
`HFO-1234yf
`
`5.2 vol.%
`
`Methane
`
`4.6 VO|.%
`
`HFC-152a
`
`3.9 vol.%
`
`Eg‘){i'§e"°
`
`3.0 vol.%
`
`Acetylene
`
`ro ane
`p
`
`2.5 vol.%
`2 1
`l %
`. vo .
`
`Gasoline
`
`1.6 vol.%
`
`.....,,.,
`
`HFO-1234yf Is Less Flammable Than 152a
`
`

`
`‘
`
`The miracles ofscience‘
`
`Burning Velocity
`
`Honeywell
`
`.aroam. r-‘nan
`4.5-on-in:un'Quuv
`rv )vv—4;
`
`Final Technical Report
`
`on Flammability Assessment of 123-lyf
`
`Appendix
`
`Example of schlieren photography method
`1234yr, 7.75 as (4: =1),P,. = 760 Torr, T,. =291.45 K
`
`Kenji Takizawa
`
`National Institute of
`
`(1)r=0ms
`
`(2)t=50ms
`
`(3)r=100ms
`
`
`
`(6)1=300ms
`(5)z=200rns
`(4)t=15oms
`Flame radi in the horizonul direction (n) were measured to minimize the efiect of buoyancy.
`In th case I used the data from l= 50 to 150 ms, durhg which the flame trontwas not
`affected by any objects
`o-—ew-u A%D{HlKMm%I&£Et$'l\
`
`Buming velocity as a function of
`(a) concentration and (b) equivalence ratio
`
`_
`Burning Velocity Measurements
`
`Advanced Industrial Science and Technology (AIST)
`
`
`
`experimental data
`—1ltting cirve by ea. (4
`
`11
`no
`Conc9nlIalion.vol%
`
`12
`
`o.eo_91.o11121.a141>1e
`o
`
`By fitting all the data to a paraboric function (4), maximum S..- was obtained as
`1.52 cm 5" at 0- =1.32. Therefore. the maximum S00 is 1.5 cm s’ at ca. 10 vol%.
`
`Sm = Sauna: "’ 51 (ll - °rrax)2
`
`(4)
`
`- Measurements performed in 3 liter spherical apparatus
`
`- Experimental result for HFO-1234yf: 1.5 cm s“
`
`-
`
`ISO 817 Flammability Classification is 2L
`(lowest flammable class classification)
`
` IQ:E‘4'.“;
`
`

`
`The miracles ofscience"
`
`Honeywell
`
`Minimum Ignition Energy
`
`- 12-liter glass sphere used in ASTM E681 flammability limit tests was modified for MIE
`testing in order to eliminate potential wall quenching effects seen in standard 1 liter
`
`vesse
`
`- Materials Tested:
`
`— HFC-32 from 16-22% (vlv) in 1% increments at 30 and 100 mJ nominal
`
`— HFO-1234yf from 7.5-11% (vlv) in 0.5% increments up to 1000 mJ nominal
`
`— Ammonia at 22% (v/v) at 100 and 300 mJ nominal
`
`Refrigerant
`
`No Ignition Occurred
`
`Ignition Occurred
`
`HFC-32
`
`30 +/— 12 mJ
`
`100 +/— 30 mJ
`
`Ammonia
`
`100 +/— 30 mJ
`
`300 +/— 100 mJ
`
`HFO-1234yf
`
`5,000 +/— 350 mJ
`
`10,000 +/— 350 mJ
`
`HFO-1234yf Is Very Difficult To Ignite With Electrical Spark
`
`

`
`The miracles ofscience-
`
`Honeywell
`
`HFO-1234yf Mild Flammability Properties
`
`UFL'
`
`A
`
`(vol%)
`
`(vol%)
`
`(vol%)
`
`2.2
`
`3.9
`
`14.4
`
`1 5
`
`HFO-1234yf 6.2
`
`10.0
`
`16.9
`
`29.3
`
`28
`
`12.3
`
` LFL'
`
`MIE
`
`(mJ)
`
`0.25
`
`0.38
`
`30-100”
`
`7.8
`
`13.0
`
`14.9
`
`13
`
`1 00-300*’
`
`5.8 5,000-10,000”
`
`BV°
`
`(cmls)
`
`46
`
`23
`
`6.7
`
`7.2
`
`1.5
`
`‘Flame |imi13measured at21 C.ASTM 681-01
`
`‘Treats conducted in 12 litre flask to minimize wall quenching effects
`‘Burning Velocity ISO 817 (HFO-1234yfBV measured by AIST, Japan)
`
`R;-=[ (KW-)_]]x£
`
`M
`IfL
`R172 _—. {(, [(0171, x LFL 1- LFL)/ LFL}x Qst x $24
`
`Cst = Stoichiometric composition in air. voI.%
`
`Q = Heat of Combustion per one mole
`
`Qst = Heat of Combustion per one mole of the
`
`

`
`Honeywell
`Autoignition Temperature &
`O
`
`I Themtraclesofsclencr
`
`- The autoignition temperature of
`HFO-1234yf was detennined at
`Chilworth Technology in UK.
`— Uniformly heated 500 ml glass flask,
`
`observed in dark for 10 mins.
`
`— Autoignition temperature for HFO-
`1234yf determined to be 405°C.
`
`- Note that the air refrigerant mixture
`must be at this temperature for
`ignition to occur.
`
`V
`
`i:iԤ~j:v
`
`234yf Passed OVVE"
`
`- Experiments were conducted to
`evaluate the ignition potential Of hot
`surfaces (up to 800°C) to cause
`ignition
`«om
`— 6 .mm sreeu mate
`Wm? p':°_pane'°xygen torch
`— No lgl1|t|Ol‘l seen
`
`- HFO-1234yf vapor sprayed onto the plate
`- Infrared Thermometer measured temperature.
`- Three “dots” seen are to aim the thermometer
`;:$:';::'::;;:::‘:::h:'::;*:;‘:2‘::33::1:’:
`refractive index gradient (caused by hot air I cold
`refrigerant),
`
`

`
`Honeywell
`
`The miracles ofscience-
`
`
`
`Summary of Hot Plate Tests
`
`HFO-1234yf
`
`Spray
`No oil
`
`Premixed with air
`
`no oil
`
`with
`
`PAG oil
`
`Spray
`no oil
`
`R-134a
`
`Premixed with air
`
`no oil
`
`with
`
`PAG oil
`
`550°C
`
`Faint Red
`
`Hot Manifold
`
`800°C
`
`Cherry Red
`
`>900°C
`
`Orange
`
`No ignition
`
`No ignition
`
`No ignition
`
`Not tested
`
`No ignition
`
`No ignition
`
`No ignition
`
`No ignition
`
`Ignition
`
`No ignition
`
`No ignition
`
`No ignition
`
`Not tested
`
`No ignition
`
`No ignition
`
`No ignition
`
`No ignition
`
`Ignition
`
`

`
`Honeywell
`
`The miracles ofscience"
`
`HFO-1234yf lgnitability to Spark from 12-V
`Battery Short Circuit
`
`- A potential ignition source for potentially flammable refrigerant/air
`leaks in passenger compartment of cars is a spark caused by a
`short circuit from a 12-V battery located under the seat
`
`- The purpose of these tests is to determine whether such a spark is
`capable of igniting an ‘optimum’ concentration of HFO-234yf in air
`
`- Follow procedures from ASTM E681 to prepare a well-blended
`refrigerant/air mixture of a known concentration in a sealed 12-I
`spherical flask; add moisture equivalent to 50% RH at 23° C
`
`- Create a short-circuit in the mixture by discharging a high-capacity
`12-V automotive battery (1020 cranking amps) across 9.5 mm
`diameter copper electrodes located in the sphere
`
`- Perform tests for 8.13, 8.5, and 9.0% HFO-1234yf concentrations at
`20°C» 60°C and 80°C; non-ignitions to be confirmed by nine (9)
`additional trials
`
`

`
`Battery Ignition Apparatus
`
`Honeywell
`
`The miracles of science '
`
`
`
` ‘I’
`.,c
`u up u.
`9.5 mm Stationary
`
`
`
`Copper Electrode
`” C
`“
`'
`
`U
`
`K
`
`Copper Electrode
`in
`~
`""
`
`
`
`
` Moveable 9.5 mm
`
`I 2-! Sphere
`
`Containing I234_yf/A ir
`
`r
`I
`
`v V
`
`.
`
`.
`
`
`
`
`
`
`1 Automotive _
`Cables
`
`
`
`‘I High Carrent ‘
`
`
`12- V Switch
`Battetjy ?
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`12- V/I020 CA
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`

`
`T'he miracles ofscience‘
`
`Honeywell
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`
`
`Battery Ignition Results
`
`- No ignitions observed at 8.13, 8.5, and 9.0% HFO-1234yf at
`either 20°, 60° or 80°C (10 trials per concentration)
`
`- For comparison the ignitability of ammonia, a refrigerant of
`relatively low flammability, was tested at a 20% v/v concentration
`at 20°C and 60° C; positive test was obtained on the first trial
`
`

`
`The miracles ofscience-
`
`Honeywell
`
`
`
`Passenger Compartment Evaluations
`
`- As shown in the previous charts, the flammability
`parameters were conducted under very tightly
`controlled conditions.
`
`— Well mixed, uniform concentration of refrigerant and air.
`
`— Stagnant, not flowing environment.
`
`— Fixed conditions (e.g. temperature)
`
`- In actual applications these conditions do not exist.
`
`- Evaluations both experimental and with computer
`simulations were conducted to try to more closely
`approximate real world conditions.
`
`

`
`F
`
`iclesofscience" CFD M 9IIn
`
`.
`
`p
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`.
`
`ng
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`
`
`.._.._:.—~~...._.
`
`—
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`Elec. Arc
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`Butane lighter
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`- Good agreement between
`prediction and measurements.
`
`- No flame from Electrical Arc.
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`- No increase in flame length from
`butane lighter.
`
`
`
`

`
`Mock-up Test Example
`
`Honeywe"
`
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`
`emzmaesorsc.-ence~
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`
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`Extreme Leak Results: No Ignition with Arc Welder
`
`- With simulated ruptured tube leak
`- No ignition with are welder on floor (simulating battery ignition source)
`— No ignition with arc welder at vent outlet (simulating PTC heater ignition
`source)
`
`

`
`The miracles ofscience-
`
`Honeywell
`
`
`
`Results of Mock-up Flammability Tests
`
`Test Description
`
`Ignition source
`
`Time of I 2 nition
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`Large Corrosion Leak (0.5 mm diameter)
`
`
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`Butane Ii 2 hter
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`5 i3 s
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`Butanolihter
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`
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`52 E S
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`Fou minutas after
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`Nolnilion-onl flarnecolorcha noted
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`3E ag;
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`No ,-.
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`ms§§§§Q!!! utanel hterfalledtoll
`
`ition-on flameoolorcha noted Butane lihterfalled to Ii ht.
`
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`5H37:;
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`'«F:54%§ -E9.
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`P-T2E .:§ 32 8
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`
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`No flame extension
`
`

`
`The miracles ofscience"
`
`Honeywell
`
`
`
`CFD Modeling & Flammability Testing Conclusions
`
`- CFD Modeling
`
`— Good agreement for refrigerant concentration profiles between CFD
`and mock—up tests
`
`- Mock-up test results
`
`—— Ignition of HFO-1234yf did not occur, even with:
`
`- worst case leak representing evaporator rupture where LFL was exceeded
`
`- high energy ignition sources (butane lighter and arc welder)
`
`- Results of hot surface tests at 800 C simulating engine
`compartment hot manifold showed no ignition.
`
`— Consistent with engine compartment test results from the CRP-1234
`program
`
`- No ignition occurred from 12V battery spark
`
`- This is likely due to low burning velocity and high MIE of HFO-
`1234yf which makes it difficult to sustain and propagate a flame