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EnovateTM (HFC-245fa) Blowing AgentSolsticeTM Liquid Blowing Agent
SolsticeTM Gaseous Blowing AgentTechnical Update
Honeywell.com����
Honeywell – a History of Innovation
HCFC
Phase-out
CFC
Phase-out
F-Gas Regulation
MONTREAL PROTOCOL EU LEGISLATION
KYOTO PROTOCOL
Innovating to enable industries’ compliance
CFCs OlefinsHCFCs HFCs
Ozone Depletingand Very High Global
Warming Potential
Non-Ozone Depleting but High Global Warming
Potential
Low-Global-Warming Potential and No Ozone
Depletion Effect
22
Honeywell.com����
Solstice Liquid Blowing Agent: 1233zd(E)
CC
HCl
• (E) 1-chloro-3,3,3-trifluoropropene
• (E) CHCl=CH-CF3
• Trans or E (entgegen) isomer
Physical Properties
Solstice LBA 141b Enovate
Mol. Wt. 130 117 134
Boiling Point, oC 19 32 15
Flame Limits, % by volume in air
None 7.6-17.7 None
Flash Point None None None
Environmental Properties
3
CF3H
Short Life = Ultra Low Environmental
Impact
Environmental Properties
Solstice LBA
141b Enovate
Atmospheric Life 26 days 9.3 yr 7.6 years
ODP ~0* 0.11 ~ 0*
GWP100 < 7 725 1030
VOC, USA reg No (est.) No No
Toxicity / OEL 300ppm** 500ppm 300ppm
*No impact on depletion of ozone layer and is commonly referred to as zero (0)
(Wuebbles , Private Communication)
** Internal HON OEL
Solstice LBA: Short Lifetime in Atmosphere � Ultra Low Environmental Impact
Honeywell.com����
Solstice Gas Blowing Agent: 1234ze(E)
CC
HCl
• (E) 1,3,3,3-trifluoropropene
• (E) CHF=CHCF3
• Trans or E (entgegen) isomer
Physical Properties
Solstice GBA 134a
Mol. Wt. 114.0 102.0
Boiling Point -19oC (-3oF) -26oC (-15oF)
Flame Limits None None
Flash Point None None
Environmental Properties
F
CF3H
Short Life = Ultra Low Environmental
Impact
Environmental Properties
Solstice GBA 134a
Atmospheric Life 14 days 7.6 years
ODP ~0* ~ 0*
GWP100 < 6 1030
VOC No (est.) No
Toxicity / OEL 1000ppm** 300ppm
*No impact on depletion of ozone layer and is commonly referred to as zero (0)
(Wuebbles , Private Communication)
** Internal HON OEL
Solstice GBA: Short Lifetime in Atmosphere � Ultra Low Environmental Impact
5
Appliance Foam Evaluations
Honeywell.com����
Commercial Appliance Trial Results
�Trial run with major global OEM and major global systems house
– Commercially manufactured household refrigerator
– 32 complete units
– Conventional foam equipment, existing in the factory
• No modifications to the process or equipment
�Solstice LBA processed very similarly to Enovate (245fa)
– Comparable in all aspects to world scale processing parameters
6
– Comparable in all aspects to world scale processing parameters
– Foam density: nearly identical
– Minimum fill weights: nearly identical
– Demold time: equal / improved
– HIPS Liner compatibility excellent even after 2 years
Solstice LBA processes similar to Enovate in refrigerator/freezer applications
Honeywell.com����
Solstice LBA PUR Cabinet Lambda Data
7
Solstice LBA optimized: 8% improvement over Enovate baseline
EnovateEnovate EnovateEnovate
Honeywell.com����
DOE Energy Performance Assessment
• DOE Energy Test Method
• Sets of 5 refrigerators: Solstice LBA and Enovate Blowing Agent baseline
Enovate Enovate
8
Solstice LBA Refrigerators: DOE Standard minus 29.5% Energy RatingSolstice LBA Refrigerators: 4% system energy improvement over baseline Enovate
2%
29.5%
Honeywell.com����
23
Solstice LBA versus 141b
Foam performance of Solstice LBA
• Polyol miscibility equal to 141b, improved compared to Enovate Blowing Agent
• Similar strength properties to Enovate, improved compared to 141b at equal density
• Improved k-factor than Enovate foams
• Improved k-factor compared to c-pentane foams
8
10
% C
han
ge i
n E
nerg
y
141b
Lambda Performance Energy Performance
Solstice LBA foam
15
16
17
18
19
20
21
22
-20 -10 0 10 20 30 40 50
Enovate
c-Pentane
HCFC-141b
Solstice LBA
La
mb
da
, m
W/m
K
Mean Temperature, oC
Lambda and Energy Performance Superior to 141b, CP, and Enovate
Source: AHAM 3rd Gen BA study plus Hon data on Solstice LBA
13
-4
-2
0
2
4
6
8
Solstice LBA Enovate c-Pentane
% C
han
ge i
n E
nerg
y
Co
nsu
mp
tio
n v
s141b
Solstice LBA foam- 3% improved vs 141b- 4% improved vs 245fa- 12% improved vs cyclopentane
Honeywell.com����
Blowing Agents ComparisonEnovate Enovate
Blowing AgentSolstice LBA
Energy Efficiency
Lower Cost/Unit
Adoption Capital/ Ease
Co
st
eff
ecti
ve
Perf
orm
an
ce HydroHydro
CarbonsHCFCHCFC141b
In-Place λλλλ
(mW/mK @ 24°C)
• 141b 17
• c-pentane 20-21
• Enovate 18-
19
• Solstice 17-18
Flammability
Toxicity
En
vir
on
men
tC
ost
eff
ecti
ve
Safe
ty
Ozone Depletion Impact
Global Warming Impact(Direct)
Volatile Organics
* Specifics will vary by energy efficiency standards and type of refrigerator
Solstice LBA: application economics, most efficient & environmentally-superior
15
Spray Foam Evaluations
Honeywell.com����
Spray Trial Formulation
ComponentsEnovate
phpSolstice LBA
php
Mannich polyether polyol 40.0 40.0
Aromatic polyester polyol 60.0 60.0
Silicone Surfactant 2.0 2.0
Amine catalysts 2.0 2.0
Solstice LBA used in existing generic industry formulation
Amine catalysts 2.0 2.0
Metal catalysts 4.1 4.1
Flame retardant 20.0 20.0
Water 2.0 2.0
Enovate Blowing Agent 20.0 -
Solstice LBA - Equal molar
Index 130 130
12
Honeywell.com����
Formulation Properties - Vapor Pressure
80
100
120
140
160
180
Pre
ssu
re, kp
a
Lower Vapor Pressure Means:
• Less potential for bulging drums
• Potential to use lower - 41%
- 31%
- 26%Enovate Blowing Agent
Solstice LBA
0
20
40
60
80
22 33 43 54
Pre
ssu
re, kp
a
Temperature, °C
Solstice LBA formulation has significantly lower vapour pressure at all temperatures
• Potential to use lower
gauge drums
• Less potential for blowing
agent loss from system
- 59%
13
Honeywell.com����
Formulation Properties - Stability
15
20
25
30
Solstice LBA Formulation Stability @ 54 °C
Enovate Blowing Agent
Solstice LBA
Gel T
ime, S
ec
Solstice LBA Formulation Stability @ 23C• Solstice LBA
formulation shows acceptable gel time variation at 54 °C
0
5
10
0 1 2 4Time @ 54 °C, Weeks
Gel T
ime, S
ec
Solstice LBA formulation has acceptable stability
• Solstice LBA formulation shows no gel time variation at RT
4 Weeks 8 Weeks
Time @ 23C
0 Weeks
14
Honeywell.com����
Lambda of Foam Sprayed @ 25°C Room Temperature
• Initial lambda• Solstice LBA 5 to 8%
lower than Enovate
• Aged lambda• Solstice LBA 4 to 8%
lower than Enovate
24
26
28
30
32
Lam
bd
a, m
W/m
K
Solstice LBA produces spray with improved lambda vs Enovate
16
18
20
22
4 24 33
Lam
bd
a, m
W
Mean Temperature , oC245fa Initial Solstice LBA Initial
245fa 28 Day Solstice LBA 28 Day
Initial Aged Initial Aged Initial Aged
15
Enovate Initial
Enovate 28 days
Honeywell.com����
Solstice LBS Versus 141b in Spray Foam
Initial Thermal Conductivity
19,0
19,2
19,4
19,6
19,8
20,0L
am
bd
a, m
W/m
K
Solstice LBA shows superior performance to 141b and Enovate Blowing Agent
18,0
18,2
18,4
18,6
18,8
19,0
141b 245fa Solstice LBA
Lam
bd
a, m
W/m
K
16
Enovate
Panel Foam Evaluations
Honeywell.com����
Polyol Blend (B-side)
Components (php) Solstice LBA Enovate cyclopentane 141b
Polyether Polyol 65.0
Polyester Polyol 35.0
Catalyst 2.0
Chinese Generic Discontinuous Panel Formulations
Surfactant 1.5
Flame Retardant 22.0
Water 2.0
Blowing Agent 23.3 24.0 12.5 21.0
Isocyanate (A-side)
PMDI 143.6
A Blowing Agent “Drop-in” Replacement Study was Conducted
18
Honeywell.com����
Cold (-29oC), 28 days
Hot (90oC), 28 days
Hot/Humid (70oC/95%RH), 28 days
Dimensional Stability
Comparison of Physical Properties
Parallel Perpendicular
Comparable Properties to Enovate, Better Properties than Cyclopentane
Compressive StrengthSolstice LBA
Cyclopentane
141b
Enovate
19
Honeywell.com����
Initial Thermal Conductivity
0,15
0,16
0,17
0,18
Th
erm
al C
on
du
cti
vit
y/f
t2.h
.oF
)
Th
erm
al C
on
du
ctiv
ity(m
W/
21.6
23.1
24.5
26.0
Cold Chain Applications 4%
8%
Cyclopentane
0,11
0,12
0,13
0,14
20 40 60 80 100 120
Temperature (°F)
Th
erm
al C
on
du
cti
vit
y(B
tu.i
n/f
t
Th
erm
al C
on
du
ctiv
ity/m
K)
15.9
17.3
18.7
20.2
oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC
Temperature
Best Thermal Insulation Performance for Cold Chain Applications
oF oF oF oF
Enovate
Solstice LBA
Cyclopentane
141b
20
Honeywell.com����
28 Day Aged Thermal Conductivity
0,15
0,16
0,17
0,18
Th
erm
al C
on
du
cti
vit
y/f
t2.h
.oF
)
Th
erm
al C
on
du
ctiv
ity(m
W/
21.6
23.1
24.5
26.0
6%
10%
21%
Enovate
Cyclopentane
141b6%
0,11
0,12
0,13
0,14
20 40 60 80 100 120
Temperature (°F)
Th
erm
al C
on
du
cti
vit
y(B
tu.i
n/f
t
Th
erm
al C
on
du
ctiv
ity/m
K)
15.9
17.3
18.7
20.2
oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC
Temperature
Cold Chain Applications
oF oF oF oF
Best Thermal Insulation Retention at All Evaluated Temperatures
Enovate
Solstice LBA
6%
21
Honeywell.com����
Solstice LBA in Panel Foam
Initial Thermal Conductivity Vs Temperature
18
20
22
La
mb
da
, m
W/m
K
HBA-2 shows superior performance to 141b and Enovate
12
14
16
13 24Mean Temperature, oC
141b Enovate Solstice LBA
La
mb
da
,
22
Solstice LBA / Cyclopentane Blends
Honeywell.com����
Comparison of Physical Properties
Cold (-29oC), 28 days
Hot (90oC), 28 days
Hot/Humid (70oC/95%RH), 28 days
Dimensional Stability
Solstice GBA/C-C5 Blend: Balanced Solution for Cost and Physical Properties
Parallel Perpendicular
Compressive Strength
100/075/25
0/10050/50
Solstice LBA/Cyclopentane Mol. Ratio
24
Honeywell.com����
Solstice LBA/Cyclopentane Blends
Initial Thermal Conductivity
0,15
0,16
0,17
0,18
Th
erm
al C
on
du
cti
vit
yB
tu.i
n/f
t2.h
.oF
)
Th
erm
al C
on
du
ctiv
ity(m
W/
21.6
23.1
24.5
26.0
Cold Chain Applications
0/100Mol. Ratio
0,11
0,12
0,13
0,14
20 40 60 80 100 120
Temperature (°F)
Th
erm
al C
on
du
cti
vit
y(B
tu.i
n
Th
erm
al C
on
du
ctiv
ity/m
K)
15.9
17.3
18.7
20.2
oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC
Temperature
Solstice LBA/Cyclopentane Blend: Balanced Solution of Cost and k-factors
oF oF oF oF
100/0
0/100
75/2550/5025/75
25
Honeywell.com����
28 Day Aged Thermal Conductivity
0,15
0,16
0,17
0,18
Th
erm
al C
on
du
cti
vit
yB
tu.i
n/f
t2.h
.oF
)
Th
erm
al C
on
du
ctiv
ity(m
W/
21.6
23.1
24.5
26.0
0/100
50/50
25/75
75/25
Solstice LBA/Cyclopentane Blends
0,11
0,12
0,13
0,14
20 40 60 80 100 120
Temperature (°F)
Th
erm
al C
on
du
cti
vit
y(B
tu.i
n
Th
erm
al C
on
du
ctiv
ity/m
K)
15.9
17.3
18.7
20.2
oF oF-6.7 oC 4.4 oC 15.6 oC 26.7 oC 37.8 oC 48.9 oC
Temperature
Addition of Solstice LBA Enhanced Thermal Insulation Retention
Cold Chain Applications
oF oF oF oF
100/0
50/5075/25
Mol. Ratio
26
Honeywell.com����
Foam Flammability Evaluations
DIN 4102-1:Class B2
15
20
Fla
me
He
igh
t, c
m
Fail
Solstice LBA: Enhanced Foam Fire Retardancy
0
5
10
100/0 75/25 50/50 25/75 0/100
Fla
me
He
igh
t, c
m
Pass
Solstice LBA/Cyclopentane Blend, Mol. Ratio
37
Gas Blowing Agent EvaluationsSolstice GBA in Panel Applications
Honeywell.com����
Comparison of Physical Properties
Cold (-29oC), 28 days
Hot (90oC), 28 days
Hot/Humid (70oC/95%RH), 28 days
Dimensional Stability
Compressive Strength
Solstice GBA
FlexuralStrength
Solstice GBA: Similar Physical Properties to 134a in Commercial Formulation
134a
29
Honeywell.com����
0,15
0,16
0,17
0,18
Initial Thermal ConductivityT
herm
al C
on
du
cti
vit
yB
tu.i
n/f
t2.h
.oF
)
Th
erm
al C
on
du
ctiv
ity(m
W/
21.6
23.1
24.5
26.0
5%
134a
Solstice GBA
0,11
0,12
0,13
0,14
20 30 40 50 60 70 80
Temperature (°F)
Th
erm
al C
on
du
cti
vit
y(B
tu.i
n
Th
erm
al C
on
du
ctiv
ity/m
K)
15.9
17.3
18.7
20.2
oF oF
-6.7 oC -1.1 oC 10.0 oC
Solstice GBA: 4% - 5% Better Thermal Insulation Value
oF oF oF oF oF
4.4 oC 15.6 oC 21.1 oC 26.6 oC
Temperature
4%
41
Honeywell.com����
Toxicity / Registration / Commercialization Status
Solstice LBA
• Toxicity – nearly complete
• Global Registrations– U.S.: SNAP / PMN applications filed
with U.S. EPA � under review
– EU: REACH registration in-process
• Current REACH registration to 10 tonnes
– Japan: Registration complete
Solstice GBA
• Toxicity – Complete
• Global Registrations• U.S.: SNAP / PMN approvals complete –
commercial sales can commence
• EU: REACH registration process underway
– Current REACH registration to 10 tonnes– Japan: Registration complete �commercial sales can commence
• Japan Chemical Substances Control
Law
– ROW Registrations to meet regional commercialization needs
• Solstice LBA registration complete:
Mexico and India
• Commercialization– Semi-commercial – late 2012
– Commercial - 2013
– Current REACH registration to 10 tonnes
• Japan: Registration complete �commercial sales can commence
– Japan Chemical Substances Control Law
• ROW Registrations to meet regional commercialization needs
– Solstice LBA registration complete: Mexico
and India
• Commercialization– Semi-commercial - NOW
– Commercial - 2013Low environmental impact solutions will meet regulatory needs timing
31
Honeywell.com����
Conclusions
• In foams, both molecules perform better than third generation benchmarks
• Solstice GBA
• 5% better thermal conductivity than 134a
• Comparable physical properties
• A environmentally sustainable and safe product
• Low GWP: Solstice GBA is < 6; Solstice LBA is < 7
• Both are not flammable
• Comparable physical properties
• Solstice LBA
• Lowest thermal conductivity and best thermal insulation retention
• Comparable dimensional stability to Enovate and better than cyclopentane
• Solstice LBA/Cyclopentane Blend
• A solution for formulation flexibility, but the blowing agent blend is most likely flammable
• Commercialization Status
• Solstice GBA is commercialized, Solstice LBA will be commercialized in late 2012
Solstice LBA or GBA: The Best Choices for Panel Foams
43
z
Enovate™ blowing agent HFC-245fa blending solutions
Shanghai Lab
Honeywell.com����
Technical development background
• China updated energy efficiency standards,
– China appliance OEMs to face technical limits with CP system
• 245fa/CP technology is becoming a major solution for China appliance industry
• 245fa/CP technology provides an optimal combination of performance and cost
• Honeywell is the leader in 245fa/CP blend development and has IP for 245fa/CP applicationapplication
• Honeywell has comprehensive technology solution for 245fa/CP application
- Strong development capability
- Good relationship with system house and equipment supplier
- Offers refrigerator OEMs with tailor made solution for 245fa/CP blend technology
- Offers excellent service
Honeywell is the leadership for 245fa application
Honeywell.com����
Boiling point of 245fa/CP blend
• 245fa/CP is an Azeotrope-like Blend
Blowing agent (wt%)
Boiling point at 745mmHg (°C)
245fa CP
100 0 14.6
Lower boiling point, better flowability
100 0 14.6
95~40 5~60 11.7±1
0 100 49
• The Boiling Point of Blend is Lower than 245fa and CP
* Honeywell Patent US 5,677,358
Honeywell.com����
Thermal conductivity of 245fa/CP blown foam
1.10
1.15
1.20
Relative K-factor
7 days. Foam Density ~ 32kg/m3
-fa
cto
r Solo
245fa
blown
245fa/CP
blend
blown
0.95
1.00
1.05
100 90 75 50 40 30 25 20 10
Re
lative
K-
0 25 50 60 75 90
% 245fa in blowing agent blend
% CP in blowing agent blend
10 70 80
Better K-factor as 245fa Levels Increase
* Honeywell Patent US 5,677,358
Honeywell.com����
Dimensional stability of 245fa/CP co-blown foam
0.4
0.6
0.8
1
Dimensional stability, -20°C after 22 days. Foam Density ~ 2.0lb/ft3 (32kg/m3)V
olu
me
Ch
an
ge
, %
Better Dimension Stability as 245fa Portion Increases
-0.2
0
0.2
0.4
100 50 30 25 20 10
Vo
lum
e C
ha
ng
e,
%
0 50 70 75 80 90
% 245fa in blowing agent blend
% CP in blowing agent blend
* Honeywell Patent US 5,677,358
Honeywell.com����
245fa in Spray Applications
• Major challenges in 141b phase-out
• Cost sensitive segment (Construction)
• HC and HFC 365mfc will not be an option due to safety concerns
• Water: poor thermal insulation and adhesion
• Blowing agent comparison:
++-++-price
-++++adhesion
++-+++handling
--++++Foam cell
++
-
+
365mfc
++-++ODP
-++++insulation
++
245fa
++
HCFC-141b
++
Water
Flammable
• Blowing agent comparison:
Honeywell.com����
Spray system development
Wall system Roof system
Test Item Unit Standard Requirement 245fa foam Requirement 245fa foam
Density kg/m3 GB/T 6343 ≥35.0 37.0 ≥55.0 55.5
Thermal conductivity W/m·k GB 3399 ≤0.024 0.0208 ≤0.024 0.022
Compressive strength kPa GB/T 8813 ≥150 240 ≥300 340
Dimensional stability•-30℃•48h•
% GB/T 8811 ≤1 0.8 ≤1 ≤1
Flammability cm GB/T 8624 ≤15 12 ≤15 13
Dimensional stability
•70℃•48h•% GB/T 8811 ≤5 3.7 ≤5 3.7
Closed cell content % GB/T 10799 ≥90 93 ≥90 95
Honeywell.com����
HFC 245fa advantages in spray application
- Quicker rise
- Larger application window
- Lower operating temperature
- Less shrinkage - reversion
- Easily applies on cold surfaces
- Equivalent or better yield
- Drums used for 141b systems can be used for
systems with ~10% of 245fa
- Minimal 245fa loss during blending- Confirmed by calculation and experimentation
Honeywell.com����
245fa in Panel Applications
• Some continuous panel manufacturers switching to HC and water from 141b
• Almost all discontinuous panel manufacturers are using 141b
• Major challenges in 141b phase-out
• Water: poor thermal insulation and adhesion
• HC: high capital investment; safety
•Blowing agent comparison:
• HC: high capital investment; safety
245fa HCFC-141b 365mfc Cyclopentane
insulation ++ ++ + +
flowability ++ ++ + +
Demouldability ++ + + +
Polyol compatibility ++ ++ + -
Foam cell ++ ++ - -
Flammability ++ ++ - -
Handling + ++ - -
Adhesion ++ + + -
Price - ++ - ++
++ best + average - worst
Honeywell.com����
Panel application
HCFC-141b 245fa/HCFC-141b 245fa
A 100 100 100
B 92 92 92
CT 22 17 27
GT 67 66 73
TFT 105 105 115
FRD 26.7 25.3 27.5
filling W 500 452 437 420 454filling W 500 452 437 420 454
CD 42.2 42.6 40.8 42.8 44.8
K factor 21.69 21.52 21.45
Compressive strength122 143 124 202 194
161 186 164 244 290
Demoudability
30 min 10.5 9.9
NA
3.13
NA
33min 12.1 11.76 4.51
36min 12.43 11.57 4.46
39min 12.16 11.25 4.32
42min 11.95 10.96 4.18
Dimensional stability
-30 • -0.90% -1.11% -1.47% -1.17%
70 • 1.39% 1.30% 1.63% 0.17%
Honeywell.com����
Transitioning from Blowing Agent 141b
Cyclo-pentane
Performance
Cost-effective
Environment
Safety
Performance
Cost-effective
• May not meet emerging energy standards and may require a 2nd transition to 245fa or Solstice LBA
Current: Transition to: Assessment Future Impact
• Solution available today
• Will meet energy efficiency
Today
141b
Cost-effective
Environment
Safety
Performance
Cost-effective
Environment
Safety
245fa &
Blends
Solstice
LBA&
Blends
245fa and LBA & Blends: Low Capital and Cost Transitions
• Will meet energy efficiency standards
• Can transition to HBA2 in future to meet GWP standards
• Most energy efficient blowing agent with very low GWP (7) puts you in the best position now and in the future
2013+
Today
Honeywell.com����
Transitioning from Cyclopentane
245fa &
Blends
Performance
Cost-effective
Environment
Safety
Current: Transition to:
• While better positioned to meet new energy standards, GWP may be an issue down the road
Assessment Future Impact
Today
Cyclo-pentane
Solstice LBA & Blends
Performance
Cost-effective
Environment
Safety
• Most energy efficient blowing agent with very low GWP (7) puts you in the best position now and in the future
245fa and LBA & Blends Offer Better Solutions Than Cyclopentane
2013+
Honeywell.com����
www.honeywell.comwww.honeywell.com
"Although all statements and information contained herein are believed to be accurate and reliable, they are presented without
guarantee or warranty of any kind, expressed or implied. Information provided herein does not relieve the user from the
responsibility of carrying out its own tests and experiments, and the user assumes all risks and liability for use of the information
and results obtained. Statements or suggestions concerning the use of materials and processes are made without representation
or warranty that any such use is free of patent infringement and are not recommendations to infringe on any patents. The user
should not assume that all toxicity data and safety measures are indicated herein or that other measures may not be required.”